CN103924258A - Method for preparing lithium hydroxide through electrolysis of salt lake brine - Google Patents
Method for preparing lithium hydroxide through electrolysis of salt lake brine Download PDFInfo
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Abstract
The invention discloses a method for preparing lithium hydroxide through electrolysis of salt lake brine. The method comprises steps of (1) evaporating and concentrating original lithium containing salt lake brine through insolation in a salt pan, so as to obtain the brine with high magnesium-lithium ratio; (2) removing impurities in the brine with high magnesium-lithium ratio so as to obtain refined brine; (3) electrolyzing with the refined brine as anode liquor and lithium hydroxide solution as cathode liquor, and obtaining lithium hydroxide monohydrate solution in a cathode chamber through a cation membrane; (4) evaporating and concentrating, cooling and crystallizing, washing and drying the lithium hydroxide monohydrate solution so as to obtain lithium hydroxide monohydrate. The method can prepare a high-purity product, has low cost and high yield of lithium, is simple and is easy to control.
Description
Technical field
The invention belongs to electrolytic preparation lithium hydroxide field, particularly, the present invention relates to a kind of method of utilizing salt lake brine electrolytic preparation lithium hydroxide.
Background technology
Lithium is one of important strategic resource, in national defense industry and national development in Hi-Tech, has important strategic importance.China is a country that salt lake distributed pole is wide, and saline lake lithium resource is abundanter, only in the Yanhu District in Qinghai, just storing the lithium chloride of up to ten million tons, accelerating lithium resource exploitation, improve lithium level of industry, is China's present stage lithium industrial boom and a brand new content in research urgently.
Lithium hydroxide, can be further as producing the products such as Lithium Acetate, lithium fluoride, lithiumbromide, lithium chloride, lithium nitrate and lithium benzoate as one of preliminary working lithium product important in lithium and compound thereof.Be mainly used at present the aspects such as the electrolytic solution of lithium soap grease, Edison battery and lithium bromide refrigerator absorption liquid.The lithium soap grease of producing with lithium hydroxide, with potassium, sodium, the lubricating grease of calcium base class is compared, there is antioxygen, withstand voltage, lubricity is good, particularly working temperature is wide, stable performance during heating for multiple times-cooling-heating cycle, long service life, water resisting property is strong, at-60 ℃～300 ℃, lubricating grease viscosity changes hardly, even when a small amount of water exists, still keep good stable lubricating property, be widely used in military equipment, aircraft, automobile, lubricating of rolling mill and various mechanical driving parts, and radio detection device, precision instrument etc., especially be applied to extremely tremble with fear, extremely hot grade under adverse weather condition, in battery industry, lithium hydroxide is made an addition in the ionogen of Edison battery, nickel metal hydride battery, can extending battery life, increase charging capacity.
In addition, also for organic synthesis and the thermal barrier of pharmacy, reagent and nuclear reactor and the protective material of metallic surface; Aspects such as material used in breathing gas purification system in space vehicle, submarine and rebreather.Therefore, research and development purity is high, technique is simple, eco-friendly LiOH production method has important practical significance and vast potential for future development.
US Patent No. 3597340 provides a kind of and has produced lithium hydroxide with membrane electrolysis, (mainly containing LiCl and NaCl by the natural bittern after evaporation concentration is purified, the percentage composition of lithium chloride is 8%～30%, its quality percentage composition is greater than the quality percentage composition of sodium-chlor) injection diaphragm sell, add direct current and within the scope of suitable electric current and voltage, carry out electrolysis, electrolysis can only make partial oxidation lithium transform, and NaCl is wherein on not impact of electrolysis.Then according to LiOHH
2o is at a certain temperature in the LiCl of different content and the difference of the solubleness in NaCl solution and crystallization, through solid-liquid separation, and washing, recrystallize can obtain purer lithium hydroxide product.
US Patent No. 4036713 first concentrated brine makes lithium content reach 2%～7%, the alkali and alkaline earth metal ions beyond precipitate and separate lithium; Then by stoichiometric ratio, adding lithium hydroxide and Quilonum Retard solution to adjust brine ph is that 10.5～11.5 precipitations are removed magnesium, calcium, iron plasma, with hydrochloric acid neutralization, obtains refining bittern; Take and refine bittern and carry out electrolysis as anolyte, water or lithium hydroxide solution as catholyte, in electrolyzer, there is cation permselective diaphragm, isolation catholyte and anolyte, during lithium ion in anolyte moves to catholyte by film under galvanic action and be combined and generate lithium hydroxide with hydroxide ion, through concentrated, recrystallization, can obtain foreign matter content lower than 0.5% lithium hydroxide monohydrate.
US Patent No. 20110044882 is selected appropriate means to remove or is reduced boron, magnesium, calcium, sulfate radical and sodium in bittern, potassium plasma (as removed the boron in bittern with acidifying or organic extractant or ion exchange resin; Add lime or white lime to remove magnesium by reaction; Use oxalic acid precipitation calcium; With barium salt precipitated sulfur acid group, evaporation concentration is removed sodium salt and sylvite), then by stoichiometry, adding lithium hydroxide and Quilonum Retard solution to adjust brine ph is 10.5～11.5, precipitation is removed magnesium, calcium plasma, by ion-exchange, further reduce again the content of calcium, magnesium ion, make calcium, magnesium ion total content lower than 150ppb.Continue concentrated brine and make the massfraction of lithium reach 2%～7%, sodium, potassium are removed with chloride form precipitation, obtain refining bittern.
In electrolytic process, anolyte is refining bittern, and catholyte is water or LiOH solution; Adopt Ineos chlor-alkali FM1500 one pole film, positively charged ion can pass through film, and negatively charged ion is blocked and can not passes through.After powering up, chlorion in anolyte moves to anode and loses electric charge and produce chlorine, lithium ion enters cathode compartment and is combined into product lithium hydroxide with the hydroxide ion that water in cathode compartment is ionized into, finally, lithium chloride in anolyte is transformed into lithium hydroxide in catholyte, electrolysis can ongoing operation until the concentration of lithium hydroxide reaches 14% or approach saturation concentration.Through concentrated, crystallization, can obtain highly purified monohydrate lithium hydroxide.
Japanese Patent JP54043174 provides a kind of electrolysis Lithium Sulphate to produce the method for lithium hydroxide, be using lithium sulfate solution as anolyte, water carries out electrolysis in membrane electrolyser device as catholyte, wherein between anolyte and catholyte, use fluorine-containing cation exchange membrane, electrolysis voltage is 3～6V, current density is 1～100A/dm2, at negative electrode, can obtain mass concentration and be about 5%～10% lithium hydroxide solution, at anode, can obtain sulphuric acid soln simultaneously.
The people such as Xu Ying are with providing a kind of three Room membrane electrolysis to be prepared the method for lithium hydroxide by Lithium Sulphate, and the experimental study of this method is at the early-stage, and current efficiency is the highest only has 66.74%, and more influence factors and industrialization are produced and needed to be continued research.
Lithium hydroxide is one of preliminary working lithium product important in lithium and compound thereof, and the method for domestic production lithium hydroxide has: the lime burning method that the lithionite of take adopts as raw material; The sodium carbonate pressurization leaching method that the triphane of take adopts as raw material.Although the two production method mature technical route, technical process is simple, and streams flux is large, energy consumption is large, cost is high, environmental pollution is more serious, and quality product is difficult to reach top grade standard.The causticizing process that the Quilonum Retard of take is raw material is particularly to produce the main method of lithium hydroxide abroad both at home and abroad at present, by the water causticizing reaction between calcium hydroxide and Quilonum Retard, makes.In this causticizing process product, calcium impurities content is high, is difficult to remove thoroughly, has a strong impact on product purity, and in addition, this method purifying process is loaded down with trivial details, and facility investment is high, and production cost is higher.The lithium hydroxide that adopts calcination method to produce, although can remove the impurity such as boron, magnesium in calcination process, has improved the purity of lithium hydroxide, and Mg content makes this technical process complicated, and equipment corrosion is serious, and evaporated water is large, and energy consumption is high.
Foreign scholar starts to walk early to the research of Electrowinning lithium hydroxide technology, but advance rate is slow.Through the time of three more than ten years, produce the main method of lithium hydroxide abroad and still use Quilonum Retard causticizing process, world lithium salts major company is not still applied to this method in the suitability for industrialized production of producing LiOH.US Patent No. 20110044882 is refinements of US Patent No. 4036713, although caused the attention that electrolysis bittern is produced lithium hydroxide, and in a plurality of national applications patents, each operational condition scope is further dwindled, but just for the lower bittern of Mg content, and the treating process more complicated of bittern, current efficiency is low, what adopt is more expensive ionic membrane, and cost compare is high.Electrolysis Lithium Sulphate is produced the method for lithium hydroxide, and current efficiency is low, and energy consumption is high, and foreign ion needs to continue to optimize on the impact of current efficiency, voltage, energy consumption.
Summary of the invention
The object of the invention is to, a kind of method of utilizing salt lake brine electrolytic preparation lithium hydroxide is provided, product purity prepared by the method is high, and cost is low, and yield is high, and technique is simple.
For achieving the above object, the present invention has adopted following technical scheme:
A method of utilizing salt lake brine electrolytic preparation lithium hydroxide, said method comprising the steps of:
1) will be concentrated by salt pan solar evaporation containing the original salt lake brine of lithium, obtain high Mg/Li ratio bittern;
2) high Mg/Li ratio bittern is obtained to refining bittern through removal of impurities;
3) using and refine bittern as anolyte, lithium hydroxide solution carries out electrolysis as catholyte, by cationic membrane, at cathode compartment, obtains lithium hydroxide monohydrate solution;
4) lithium hydroxide monohydrate solution is dried through evaporation concentration, crystallisation by cooling, washing, obtain lithium hydroxide monohydrate, the mother liquor obtaining after crystallisation by cooling carries out cyclic electrolysis as electrolysis cathode liquid or for the pH of high Mg/Li ratio bittern removal of impurities regulator solution.
Preferably, described step 2) removal of impurities process is: first with hydrochloric acid, adjust its potential of hydrogen, make its pH value remain on 1.5～2.5, boron ion in bittern is separated out with boric acid form, after solid-liquid separation, add in proportion lime or white lime, fully stir, remove by filter magnesium ion and sulfate radical, obtain the electrolysis stock liquid of low boron, low-sulfur;
Then at 50～70 ℃ of temperature, adopting two-step approach demagging, is first 8.5～9.5 with the pH that lithium hydroxide is adjusted electrolysis stock liquid, the boron ion in the magnesium hydroxide of generation and excessive magnesium ion combined belt positive charge adsorbent solution, and solid-liquid separation is removed magnesium ion; Then using step 4) mother liquor that obtains after crystallisation by cooling and/or the Quilonum Retard solution pH that adjusts solution is 11.5～12.5, remove magnesium ion residual in solution, calcium ion and iron ion, with hydrochloric acid, neutralize this solution, neutralizer is concentrated into lithium ion massfraction higher than 3.6%, now, sodium-chlor and Repone K Precipitation, remove precipitation and obtain the refining bittern that lithium chloride massfraction is greater than 22%.
Preferably, ionization process described step 3) is: select domestic cationic membrane and electrolyzer, anolyte is refining bittern, its lithium chloride massfraction is greater than 22%, catholyte is lithium hydroxide solution, and its lithium hydroxide massfraction is less than 3%, and current density is 1.0～2.4kA/m
2, electrolysis temperature>=55 ℃, average working voltage is 3.0～3.4V, the hydrogen that electrolysis produces and chlorine are as byproduct.
The hydrogen reaction that the chlorine that described electrolysis produces and electrolysis produce generates hydrochloric acid, or the chlorine that electrolysis produces obtains liquid chlorine through liquefaction.
Preferably, described step 4) process is: electrolysis reaches the catholyte of nearly saturation concentration under agitation through the concentrated lithium hydroxide solid of separating out of heating evaporation, solidliquid mixture is cooled to 30～50 ℃ of crystallizations, vacuum filtration or centrifugation, obtain lithium hydroxide monohydrate, through washing, being dried and obtaining the lithium hydroxide monohydrate product that lithium hydroxide monohydrate content is greater than 99.8% at 60～90 ℃.
The present invention to the concentrated high Mg/Li ratio bittern obtaining of salt pan solar evaporation by a series of removal of impurities process, obtain refining bittern (mainly containing LiCl, massfraction is greater than 22%), impurity ion content is (Mg+Ca)≤1ppm, NaCl%≤5% (wt%).
The present invention is usingd and is refined bittern as anolyte, certain density lithium hydroxide solution carries out electrolysis as catholyte, by the selection perviousness of cationic membrane, at cathode compartment, obtain lithium hydroxide monohydrate solution, catholyte is dried through evaporation concentration, crystallisation by cooling, washing, can obtain lithium hydroxide monohydrate product, product purity is greater than 99.8%, and lithium yield approaches 100%.
The pH that the present invention adjusts solution with lithium hydroxide is 8.5～9.5, the boron ion in the magnesium hydroxide of generation and excessive magnesium ion combined belt positive charge adsorbent solution, and solid-liquid separation can be removed most magnesium.
The present invention also can utilize the ion exchange resin of effects of boron resin and magnesium, calcium to remove boron ion, magnesium ion and the calcium ion in solution.
The present invention adds direct current and carries out electrolysis, and electrolytic anode liquid is ionized into Li in electrolyzer
+and Cl
-, Li wherein
+under charge effect, by thering is optionally cationic membrane, move to cathode compartment, the Cl-staying generates chlorine under anode electrolysis effect.Water power in cathode compartment is from becoming H
+and OH
-, OH wherein
-there is the Li that optionally cationic membrane gear is come in cathode compartment Yu Cong anolyte compartment
+be combined into product lithium hydroxide, H
+under catholyte effect, generate H
2.Current efficiency is higher than 75%, and average working voltage is at 3.0～3.4V, and the hydrogen that electrolysis produces and chlorine can be used as byproduct and is used.The a small amount of sodium-chlor containing in anolyte lithium chloride does not exert an influence to electrolysis and product, separated according to electrolysis index and the controlled hydrogen manufacturing sodium oxide of the physical property of product and lithium hydroxide in electrolytic process, mother liquor after sodium hydroxide solution and the separation of part catholyte condensing crystal removes to adjust the pH of solution in refining bittern process, and lithium hydroxide solution can obtain lithium hydroxide monohydrate product through concentrated.
Technique of the present invention is simple, is easy to control, and operational reliability is high, and the lithium hydroxide product purity obtaining is high, can be directly used in the lithium source of lithium soap grease, battery industry and other lithium product, need not again purify.
The present invention utilizes salt lake brine electrolytic preparation lithium hydroxide monohydrate, and current efficiency is higher than 75%, and average working voltage is at 3.0～3.4V, and product purity is greater than 99.8%.
The present invention has eliminated public hazards and environmental pollution that diaphragm process is used asbestos, mercury process to use mercury to cause.
What the present invention is directed to is the salt lake brine of high Mg/Li ratio, and the impurity-removing method in brine refining process is fairly simple, has adopted domestic cationic membrane (as Eastern Mountain DF988) during electrolysis, and the rate of recovery of lithium is high, and cost compare is low, non-secondary pollution.
The present invention compared with prior art has the following advantages:
1) product purity is high: in electrolytic chlorination lithium solution of the present invention, do not introduce other ion, in the product obtaining, foreign matter content is low.
2) cost is low: electrolyzer and ionic membrane are all domestic, and price is lower.
3) yield of lithium is high: anolyte cyclic electrolysis, and the yield of lithium approaches 100%; The mother liquor of catholyte after evaporation concentration, solid-liquid separation can carry out cyclic electrolysis as catholyte again.
4) technique is simple and easy to control: the salt lake brine removal of impurities to selective separation high Mg/Li ratio is simple, electrolytic refining bittern, and its technique is simple, is easy to control, and operational reliability is higher, applied widely.
5) can control the impact of sodium-chlor on product purity in anolyte during electrolysis.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
The Qinghai magnesium sulfate of take is raw material containing lithium magnesium chloride saturated bittern, by specific examples, the method for electrolytic preparation lithium hydroxide of the present invention is described further.
As shown in Figure 1, will be concentrated by salt pan solar evaporation containing the original salt lake brine of lithium, obtain high Mg/Li ratio bittern.It consists of (g/L): Li5.11, Mg124.02, Ca0.82, Na1.93, K0.91, Cl334.79, SO
4 2-35.60, H
3bO
351.4, the high Mg/Li ratio bittern obtaining obtains lithium hydroxide monohydrate through removal of impurities, electrolysis, evaporation, crystallization.
Embodiment mono-
(1) preparation of refining bittern
First the bittern of the concentrated saturated magnesium chloride obtaining of salt pan solar evaporation adjusted to its potential of hydrogen with hydrochloric acid, make its pH value remain on 1.5, in bittern, boron is separated out with boric acid, after solid-liquid separation, add in proportion lime or white lime, fully stir, remove by filter magnesium and sulfate radical, obtain the electrolysis stock liquid of low boron, low-sulfur.Then at 50～70 ℃ of temperature, adopt two-step approach demagging, first the pH that adjusts solution with lithium hydroxide is 8.5, boron ion in the magnesium hydroxide generating and excessive magnesium ion combined belt positive charge adsorbent solution, solid-liquid separation is removed most magnesium, then with the pH of the mother liquor lithium hydroxide solution after Crystallization Separation and Quilonum Retard solution adjustment solution, be 11.5, remove remaining magnesium and calcium, iron plasma, make magnesium in bittern, calcium, iron, boron plasma is down to minimum, with hydrochloric acid, neutralize this bittern, if be necessary, recycle effects of boron resin and magnesium, the ion exchange resin of calcium continues to remove boron ion, magnesium ion or calcium ion.
Bittern to the lithium ion massfraction continuing after concentrated purification is 3.6% (counting 22% with lithium chloride), sodium-chlor and Repone K are insoluble to the concentrated brine of chloride containing lithium >=22% and Precipitation, the total concn of sodium, potassium ion is remained on below 5%, obtain refining bittern (main component is lithium chloride).
In high Mg/Li ratio salt lake brine, Mg/Li ratio is more than 40:1.
(2) electrolytic refining bittern
Select domestic cationic membrane Eastern Mountain DF988 and electrolyzer, anolyte is refining bittern, and catholyte is that massfraction is 3% lithium hydroxide solution, and current density is 1.2kA/m
2, electrolysis temperature is 55 ℃, and cathode and anode circular flow is 0.2L/min, and now, current efficiency is 75.56%, and energy consumption is 4.475kWh/kg
-1liOH, average working voltage is 3.02V, the hydrogen that electrolysis produces and chlorine can be used as byproduct and are used.
Adjust the potential of hydrogen of anolyte before electrolysis, make in its pH, between 2～3, can to suppress better oxygen evolution reaction and chlorine and to dissolve the side reaction producing.
(3) catholyte condensing crystal
Electrolysis reaches the catholyte that approaches saturation concentration under agitation can separate out lithium hydroxide solid through heating evaporation is concentrated, solidliquid mixture is cooled to 30 ℃, vacuum filtration or centrifugation, can obtain lithium hydroxide monohydrate, through washing, being dried and obtaining the lithium hydroxide monohydrate product that purity is higher at 60～90 ℃.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is greater than 99.8%, lithium yield >=99.8%.
Embodiment bis-
(1) preparation of refining bittern
First the bittern of the concentrated saturated magnesium chloride obtaining of salt pan solar evaporation adjusted to its potential of hydrogen with hydrochloric acid, make its pH value remain on 2.5, in bittern, boron is separated out with boric acid, after solid-liquid separation, add in proportion lime or white lime, fully stir, remove by filter magnesium and sulfate radical, obtain the electrolysis stock liquid of low boron, low-sulfur.Then at 50～70 ℃ of temperature, adopt two-step approach demagging, first the pH that adjusts solution with lithium hydroxide is 9.5, boron ion in the magnesium hydroxide generating and excessive magnesium ion combined belt positive charge adsorbent solution, solid-liquid separation is removed most magnesium, then with the pH of the mother liquor lithium hydroxide solution after Crystallization Separation or Quilonum Retard solution adjustment solution, be 12.5, remove remaining magnesium and calcium, iron plasma, make magnesium in bittern, calcium, iron, boron plasma is down to minimum, with hydrochloric acid, neutralize this bittern, if be necessary, recycle effects of boron resin and magnesium, the ion exchange resin of calcium continues to remove boron ion, magnesium ion or calcium ion.
Bittern to the lithium ion massfraction continuing after concentrated purification is 3.7% (counting 23% with lithium chloride), sodium-chlor and Repone K are insoluble to the concentrated brine of chloride containing lithium >=22% and Precipitation, the total concn of sodium, potassium ion is remained on below 5%, obtain refining bittern (main component is lithium chloride).
In high Mg/Li ratio salt lake brine, Mg/Li ratio is more than 40:1.
(2) electrolytic refining bittern
Select domestic cationic membrane and electrolyzer, anolyte is that lithium chloride massfraction is 23% refining bittern, and catholyte is that massfraction is 3% lithium hydroxide solution, and current density is 2.0kA/m
2, electrolysis temperature is 56 ℃, and cathode and anode circular 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, the hydrogen that electrolysis produces and chlorine can be used as byproduct and are used.
Adjust the potential of hydrogen of anolyte before electrolysis, make in its pH, between 2～3, can to suppress better oxygen evolution reaction and chlorine and to dissolve the side reaction producing.
(3) catholyte condensing crystal
Electrolysis reaches the catholyte that approaches saturation concentration under agitation can separate out lithium hydroxide solid through heating evaporation is concentrated, solidliquid mixture is cooled to 50 ℃, vacuum filtration or centrifugation, can obtain lithium hydroxide monohydrate, through washing, being dried and obtaining the lithium hydroxide monohydrate product that purity is higher at 60～90 ℃.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is greater than 99.8%, lithium yield >=99.9%.
Embodiment tri-
(1) preparation of refining bittern
First the bittern of the concentrated saturated magnesium chloride obtaining of salt pan solar evaporation adjusted to its potential of hydrogen with hydrochloric acid, make its pH value remain on 2, in bittern, boron is separated out with boric acid, after solid-liquid separation, add in proportion lime or white lime, fully stir, remove by filter magnesium and sulfate radical, obtain the electrolysis stock liquid of low boron, low-sulfur.Then at 50～70 ℃ of temperature, adopt two-step approach demagging, first the pH that adjusts solution with lithium hydroxide is 9, boron ion in the magnesium hydroxide generating and excessive magnesium ion combined belt positive charge adsorbent solution, solid-liquid separation is removed most magnesium, then with the pH of the mother liquor lithium hydroxide solution after Crystallization Separation and Quilonum Retard solution adjustment solution, be 12, remove remaining magnesium and calcium, iron plasma, make magnesium in bittern, calcium, iron, boron plasma is down to minimum, with hydrochloric acid, neutralize this bittern, if be necessary, recycle effects of boron resin and magnesium, the ion exchange resin of calcium continues to remove boron ion, magnesium ion or calcium ion.
Bittern to the lithium ion massfraction continuing after concentrated purification is 3.6% (counting 22% with lithium chloride), sodium-chlor and Repone K are insoluble to the concentrated brine of chloride containing lithium >=22% and Precipitation, the total concn of sodium, potassium ion is remained on below 5%, obtain refining bittern (main component is lithium chloride).
In high Mg/Li ratio salt lake brine, Mg/Li ratio is more than 40:1.
(2) electrolytic refining bittern
Select domestic cationic membrane and electrolyzer, anolyte is that lithium chloride massfraction is 22% refining bittern, and catholyte is massfraction 2% lithium hydroxide solution, and current density is 2.4kA/m
2, electrolysis temperature is 59 ℃, and cathode and anode circular 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, the hydrogen that electrolysis produces and chlorine can be used as byproduct and are used.
Adjust the potential of hydrogen of anolyte before electrolysis, make in its pH, between 2～3, can to suppress better oxygen evolution reaction and chlorine and to dissolve the side reaction producing.
(3) catholyte condensing crystal
Electrolysis reaches the catholyte that approaches saturation concentration under agitation can separate out lithium hydroxide solid through heating evaporation is concentrated, solidliquid mixture is cooled to 40 ℃, vacuum filtration or centrifugation, can obtain lithium hydroxide monohydrate, through washing, being dried and obtaining the lithium hydroxide monohydrate product that purity is higher at 60～90 ℃.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is greater than 99.8%, lithium yield >=99.9%.
Embodiment tetra-
(1) preparation of refining bittern
First the bittern of the concentrated saturated magnesium chloride obtaining of salt pan solar evaporation adjusted to its potential of hydrogen with hydrochloric acid, make its pH value remain on 2, in bittern, boron is separated out with boric acid, after solid-liquid separation, add in proportion lime or white lime, fully stir, remove by filter magnesium and sulfate radical, obtain the electrolysis stock liquid of low boron, low-sulfur.Then at 50～70 ℃ of temperature, adopt two-step approach demagging, first the pH that adjusts solution with lithium hydroxide is 9, boron ion in the magnesium hydroxide generating and excessive magnesium ion combined belt positive charge adsorbent solution, solid-liquid separation is removed most magnesium, then with the pH of the mother liquor lithium hydroxide solution after Crystallization Separation and Quilonum Retard solution adjustment solution, be 12, remove remaining magnesium and calcium, iron plasma, make magnesium in bittern, calcium, iron, boron plasma is down to minimum, with hydrochloric acid, neutralize this bittern, if be necessary, recycle effects of boron resin and magnesium, the ion exchange resin of calcium continues to remove boron ion, magnesium ion or calcium ion.
Bittern to the lithium ion massfraction continuing after concentrated purification is 4.6% (counting 28% with lithium chloride), sodium-chlor and Repone K are insoluble to the concentrated brine of chloride containing lithium >=22% and Precipitation, the total concn of sodium, potassium ion is remained on below 5%, obtain refining bittern (main component is lithium chloride).
In high Mg/Li ratio salt lake brine, Mg/Li ratio is more than 40:1.
(2) electrolytic refining bittern
Select domestic cationic membrane and electrolyzer, anolyte is that lithium chloride massfraction is 28% refining bittern, and catholyte is massfraction 3% lithium hydroxide solution, and current density is 1.6kA/m
2, electrolysis temperature is 65 ℃, and cathode and anode circular 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, the hydrogen that electrolysis produces and chlorine can be used as byproduct and are used.
Adjust the potential of hydrogen of anolyte before electrolysis, make in its pH, between 2～3, can to suppress better oxygen evolution reaction and chlorine and to dissolve the side reaction producing
(3) catholyte condensing crystal
Electrolysis reaches the catholyte that approaches saturation concentration under agitation can separate out lithium hydroxide solid through heating evaporation is concentrated, solidliquid mixture is cooled to 40 ℃, vacuum filtration or centrifugation, can obtain lithium hydroxide monohydrate, through washing, being dried and obtaining the lithium hydroxide monohydrate product that purity is higher at 60～90 ℃.
After testing, in lithium hydroxide monohydrate product, lithium hydroxide monohydrate content is greater than 99.8%, lithium yield >=99.9%.
Claims (5)
1. a method of utilizing salt lake brine electrolytic preparation lithium hydroxide, said method comprising the steps of:
1) will be concentrated by salt pan solar evaporation containing the original salt lake brine of lithium, obtain high Mg/Li ratio bittern;
2) high Mg/Li ratio bittern is obtained to refining bittern through removal of impurities;
3) using and refine bittern as anolyte, lithium hydroxide solution carries out electrolysis as catholyte, by cationic membrane, at cathode compartment, obtains lithium hydroxide monohydrate solution;
4) lithium hydroxide monohydrate solution is dried through evaporation concentration, crystallisation by cooling, washing, obtain lithium hydroxide monohydrate, the mother liquor obtaining after crystallisation by cooling carries out cyclic electrolysis as electrolysis cathode liquid or for the pH of high Mg/Li ratio bittern removal of impurities regulator solution.
2. the method for utilizing salt lake brine electrolytic preparation lithium hydroxide according to claim 1, it is characterized in that, described step 2) removal of impurities process is: first with hydrochloric acid, adjust its potential of hydrogen, make its pH value remain on 1.5～2.5, boron ion in bittern is separated out with boric acid form, after solid-liquid separation, add in proportion lime or white lime, fully stir, remove by filter magnesium ion and sulfate radical, obtain the electrolysis stock liquid of low boron, low-sulfur;
Then at 50～70 ℃ of temperature, adopting two-step approach demagging, is first 8.5～9.5 with the pH that lithium hydroxide is adjusted electrolysis stock liquid, the boron ion in the magnesium hydroxide of generation and excessive magnesium ion combined belt positive charge adsorbent solution, and solid-liquid separation is removed magnesium ion; Then using step 4) mother liquor that obtains after crystallisation by cooling and/or the Quilonum Retard solution pH that adjusts solution is 11.5～12.5, remove magnesium ion residual in solution, calcium ion and iron ion, with hydrochloric acid, neutralize this solution, neutralizer is concentrated into lithium ion massfraction higher than 3.6%, now, sodium-chlor and Repone K Precipitation, remove precipitation and obtain the refining bittern that lithium chloride massfraction is greater than 22%.
3. the method for utilizing salt lake brine electrolytic preparation lithium hydroxide according to claim 1, it is characterized in that, described step 3) ionization process is: select domestic cationic membrane and electrolyzer, anolyte is refining bittern, its lithium chloride massfraction is greater than 22%, catholyte is lithium hydroxide solution, and its lithium hydroxide massfraction is less than 3%, and current density is 1.0～2.4kA/m
2, electrolysis temperature>=55 ℃, average working voltage is 3.0～3.4V, the hydrogen that electrolysis produces and chlorine are as byproduct.
4. the method for utilizing salt lake brine electrolytic preparation lithium hydroxide according to claim 3, is characterized in that, the hydrogen reaction that the chlorine that described electrolysis produces and electrolysis produce generates hydrochloric acid, or the chlorine that electrolysis produces obtains liquid chlorine through liquefaction.
5. the method for utilizing salt lake brine electrolytic preparation lithium hydroxide according to claim 1, it is characterized in that, described step 4) process is: electrolysis reaches the catholyte of nearly saturation concentration under agitation through the concentrated lithium hydroxide solid of separating out of heating evaporation, solidliquid mixture is cooled to 30～50 ℃ of crystallizations, vacuum filtration or centrifugation, obtain lithium hydroxide monohydrate, the lithium hydroxide monohydrate product through washing, being greater than 99.8% at 60～90 ℃ of dry content that obtain lithium hydroxide monohydrate.
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| CN201410175543.7A CN103924258B (en) | 2014-04-28 | 2014-04-28 | The method utilizing salt lake bittern electrolytic preparation lithium hydroxide |
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Cited By (10)
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| CN105177288A (en) * | 2015-10-28 | 2015-12-23 | 中国科学院青海盐湖研究所 | Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio |
| CN106011917A (en) * | 2016-07-06 | 2016-10-12 | 北京清源创智科技有限公司 | Production method of high-purity lithium hydroxide |
| 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 |
| CN108660476A (en) * | 2017-08-10 | 2018-10-16 | 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 |
| CN109267086A (en) * | 2018-10-30 | 2019-01-25 | 吉首大学 | The device and method of magnesium/lithium separation and enriching lithium in a kind of salt lake bittern |
| CN110029354A (en) * | 2019-05-08 | 2019-07-19 | 蓝星(北京)化工机械有限公司 | Utilize the method for lithium chloride Direct Electrolysis preparation LITHIUM BATTERY lithium hydroxide |
| CN112553647A (en) * | 2019-09-25 | 2021-03-26 | 艾科斯塔纳乌科技有限公司 | Method for producing lithium hydroxide monohydrate from brine |
| CN112673119A (en) * | 2018-08-17 | 2021-04-16 | 利特科技工业有限公司 | Improved lithium processing method |
| CN112703258A (en) * | 2018-08-17 | 2021-04-23 | 利特科技工业有限公司 | Improved electrochemical cell apparatus and method for separating impurities |
| CN112830527A (en) * | 2021-04-22 | 2021-05-25 | 金驰能源材料有限公司 | Precursor of hollow cathode material and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105177288A (en) * | 2015-10-28 | 2015-12-23 | 中国科学院青海盐湖研究所 | Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio |
| CN106011917A (en) * | 2016-07-06 | 2016-10-12 | 北京清源创智科技有限公司 | Production method of high-purity lithium hydroxide |
| 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 |
| CN108660476A (en) * | 2017-08-10 | 2018-10-16 | 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 |
| 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 |
| CN112673119A (en) * | 2018-08-17 | 2021-04-16 | 利特科技工业有限公司 | Improved lithium processing method |
| CN112703258A (en) * | 2018-08-17 | 2021-04-23 | 利特科技工业有限公司 | Improved electrochemical cell apparatus and method for separating impurities |
| CN109267086A (en) * | 2018-10-30 | 2019-01-25 | 吉首大学 | The device and method of magnesium/lithium separation and enriching lithium in a kind of salt lake bittern |
| CN110029354A (en) * | 2019-05-08 | 2019-07-19 | 蓝星(北京)化工机械有限公司 | Utilize the method for lithium chloride Direct Electrolysis preparation LITHIUM BATTERY lithium hydroxide |
| CN112553647A (en) * | 2019-09-25 | 2021-03-26 | 艾科斯塔纳乌科技有限公司 | Method for producing lithium hydroxide monohydrate from brine |
| CN112830527A (en) * | 2021-04-22 | 2021-05-25 | 金驰能源材料有限公司 | Precursor of hollow cathode material and preparation method thereof |
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