CN105177288A - Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio - Google Patents

Method for preparing lithium hydroxide from salt lake brine with high magnesium-lithium ratio Download PDF

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CN105177288A
CN105177288A CN201510710663.7A CN201510710663A CN105177288A CN 105177288 A CN105177288 A CN 105177288A CN 201510710663 A CN201510710663 A CN 201510710663A CN 105177288 A CN105177288 A CN 105177288A
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lithium
magnesium
lithium hydroxide
ratio
boron
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CN105177288B (en
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王怀有
王敏
李锦丽
时历杰
赵有璟
钟远
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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Abstract

The invention relates to the field of comprehensive utilization of salt lake resources, in particular to a method for preparing lithium hydroxide from salt lake brine with the high magnesium-lithium ratio. The method includes the steps that the salt lake brine with the high magnesium-lithium ratio serves as a raw material, and a certain amount of soluble trivalent metal salt is added; the magnesium-lithium ratio of the salt lake brine with the high magnesium-lithium ratio is reduced by synthesizing magnesium-based layered function materials so that magnesium and lithium in the salt lake brine with the high magnesium-lithium ratio can be separated; the magnesium in the brine is removed, and then the lithium hydroxide is prepared through lithium-rich hydrotalcite mother liquor. By means of the method for separating the magnesium from the lithium and preparing the lithium hydroxide, the technical problems that as for original methods, technologies are complex, cost is high, the use rate of magnesium resources and the use rate of lithium resources are low, and the magnesium-lithium separating effect is not ideal can be effectively solved, technological processes for preparing the lithium hydroxide are simplified, and cost is reduced; in addition, the waste magnesium resources can be sufficiently used; meanwhile, the cost of the magnesium-based function materials is reduced, higher-value utilization and comprehensive utilization of the salt lake magnesium resources, the salt lake lithium resources and salt lake boron resources are achieved, and good industrialization prospects are achieved.

Description

A kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare lithium hydroxide
Technical field
The present invention relates to salt lake resources field of comprehensive utilization, particularly, the present invention relates to a kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare Quilonum Retard, say further, is a kind of method that in salt lake brine prepared by the separation of magnesium lithium, magnesium base functional materials and Quilonum Retard.
Background technology
Lithium is the lightest metal, is described as " energy metal promoting world's progress ".It has unique process based prediction model, is strategic resource significant in national economy and national defense construction.Occurring in nature, lithium resource is mainly composed and is stored in solid mineral and liquid brine.In the past, China carries lithium to salt lake brine and pays little attention to, and for many years, the lithium salts of China is produced and still contained lithium ore based on triphane, lithionite etc.Carry lithium due to salt lake brine and have that stock number is large, low cost and other advantages, and along with solid lithium ore resources day by day exhausted, salt lake brine becomes the main source of lithium resource gradually.
But China's Qinghai Salt Lake is different with South America " rich lithium type " salt lake from " rich potassium type " salt lake, North America, is " rich magnesium types " salt lake, has the advantages that Mg/Li ratio is high.If the magnesium lithium mass ratio in the salt lakes such as large bavin dawn, Yi Liping, East Taijinaier, West Taijinar and Cha Er Han is all more than 40 ~ 1800, the similarity of magnesium lithium character brings difficulty to the exploitation of salt lake resources.Will extract the necessary first separating magnesium of lithium from bittern, therefore international ripe " evaporation-precipitation " puies forward the constructional feature that lithium technology is not suitable for Resources of Salt Lakes In China.High Mg/Li ratio bittern carries lithium becomes the difficult point and hot issue that domestic and international academia and industrial community be concerned about jointly.Its key issue is carry out the separation and Extraction of lithium around the Mg/Li ratio how reduced in salt lake brine and launch.
Lithium hydroxide is one of preliminary working lithium product important in lithium and compound thereof, is mainly used in the many aspects such as lithium soap grease, Edison battery electrolytic solution and lithium bromide refrigerator absorption liquid.The method of domestic production lithium hydroxide has: the lime burning method of employing is that lithium hydroxide prepared by raw material with lithionite; Sodium carbonate pressurization leaching method is adopted to be that lithium hydroxide prepared by raw material with triphane.Above two kinds of method and technology routes are ripe, and technical process is simple, but streams flux is large, cost is high, energy consumption is large, environmental pollution is more serious.The lithium hydroxide adopting calcination method to produce, although can remove the impurity such as boron, magnesium in calcination process, improves 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.And causticizing process is the main method of particularly producing lithium hydroxide both at home and abroad abroad at present, this method take Quilonum Retard as raw material, is obtained by the water causticizing reaction between calcium hydroxide and Quilonum Retard.In the method product, calcium impurities content is high, is difficult to thorough removing, 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 China Patent Publication No. CN1579937A nano magnalium hydrotalcite that utilized salt lake brine to prepare, does not study the Mg/Li ratio in salt lake brine and lithium hydroxide preparation, prepares the mother liquor after nano magnalium hydrotalcite for alkalescence, and containing CO 3 2-, the production of the products such as lithium hydroxide can not be directly used in, the SO simultaneously existed in mother liquor 4 2-also the enrichment of lithium and the preparation of lithium hydroxide is unfavorable for B.High Mg/Li ratio bittern is obtained refining bittern through removal of impurities by China Patent Publication No. CN103924258A, using refining bittern as anolyte, lithium hydroxide solution carries out electrolysis as catholyte, can obtain purity higher hydrogen Lithium Oxide 98min monohydrate by ion-exchange membrane electrolysis.China Patent Publication No. CN103864249A is first by adding the calcium ions and magnesium ions in sodium carbonate removing salt lake brine; Concentrated brine is obtained after the low Mg/Li ratio bittern obtained is concentrated by common electrodialysis; Sodium carbonate calcium-magnesium removing ion is again added in concentrated brine; Add sodium carbonate by multiple steps of crystallization method afterwards and obtain Quilonum Retard; Lithium hydroxide is prepared by electrolysis-bipolar membrane electrodialysis system after Quilonum Retard is molten again.Above two kinds of methods bittern removing magnesium workshop section need a large amount of alkali, energy consumption and cost higher, waste a large amount of magnesium resources simultaneously.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method utilizing salt lake brine with high magnesium-lithium ratio to prepare lithium hydroxide is provided, product purity prepared by the method is high, cost is low, yield is high, technique is simple, achieves the high-valued and comprehensive exploitation of magnesium in salt lake resources, lithium, boron and utilization simultaneously.
The method utilizing salt lake brine with high magnesium-lithium ratio to prepare lithium hydroxide of the present invention, comprises the following steps:
1) according to Phase Diagram for Aqueous Salt Solutions principle, multistage evaporation is carried out with concentrated salt lake brine to salt lake brine, and reduce Mg/Li ratio by separating out salt, after evaporative crystallization, obtain the old halogen that Mg/Li ratio is 10 ~ 500;
2) Mg in old halogen is regulated 2+concentration, make Mg 2+concentration, at 0.5mol/L ~ 5mol/L, adds soluble trivalent metal salt and is made into mixing salt solution; Wherein, described Mg 2+be 1 ~ 5 with the cationic mol ratio of trivalent metal salt;
3) to step 2) mixing salt solution in add mixed ammonium/alkali solutions, adopt coprecipitation method under temperature is 25 ~ 70 DEG C of conditions, carry out into nuclear reaction; Carry out ageing after nucleation, Aging Temperature 50 ~ 150 DEG C, digestion time is 6 ~ 48h;
4) by step 3) mixed liquor after ageing after filtration, washing and dry, obtain magnesium based hydrotalcite and low Mg/Li ratio mother liquor; The Mg/Li ratio in mother liquor is made to drop to less than 0.1; Wherein wash water used can recycle, make after wherein lithium reaches finite concentration, washing water can with step 7) in effluent liquid be mixed for the preparation of Quilonum Retard;
5) to step 4) low Mg/Li ratio mother liquor in add certain density acid, adjust ph to 7 ~ 10;
6) by the mother liquor after adjust ph with the ion exchange column by being equipped with effects of boron resin of the flow velocity of 1 ~ 5mL/min, make boron enrichment in the ion exchange column that effects of boron resin is housed, make in effluent liquid that B content is not higher than 10ppm, the adsorption rate of boron is more than 99%;
7) with a certain amount of distilled water wash ion exchange column, until not chloride ion-containing in effluent liquid, removing residual mother liquor also obtains effluent liquid.
8) by concentration be the flow velocity eluent ion exchange column of elutriant with 1 ~ 5mL/min of 0.5 ~ 1.5mol/L, by the boron desorb in effects of boron resin, make the desorption efficiency of boron more than 99%, obtain boron-rich mother liquor;
9) carry out multistage evaporation to boron-rich mother liquor or forced evaporation concentrates, carry out crystallisation by cooling to the mother liquor after concentrated, obtained boric acid, the boric acid quality product mark of acquisition is greater than 99%, and the yield of boron is 50% ~ 90%;
10) to above-mentioned steps 7) effluent liquid in enter the hydrochloric acid of 0.5 ~ 3mol/L, regulate the pH value of effluent liquid, be neutral or slightly acidic, remove the CO in mother liquor simultaneously 3 2-;
11) in the effluent liquid after adjust ph, first add calcium chloride removing wherein most SO 4 2-, make SO 4 2-content, not higher than 500ppm, adds bariumchloride afterwards, makes SO 4 2-content is not higher than 50ppm;
12) carry out the evaporation of multistage salt pan or forced evaporation to above-mentioned solution, obtaining lithium chloride mass concentration is 20% ~ 30% rich lithium solution;
13) using rich lithium solution as anolyte, be that the lithium hydroxide solution of 1% ~ 3% is as catholyte using massfraction, be that 0.2 ~ 0.5L/min carries out electrolysis at temperature 50 ~ 70 DEG C, circular flow, obtained the lithium hydroxide monohydrate solution of nearly saturation concentration at cathode compartment by cationic membrane, before electrolysis, the pH value of adjustment anolyte is 2.5 ~ 3.5, and oxygen evolution reaction and chlorine can be suppressed better to dissolve the side reaction produced;
14) the lithium hydroxide monohydrate solution of nearly saturation concentration is through evaporation concentration, crystallisation by cooling, washing drying, and obtain lithium hydroxide monohydrate, the mother liquor obtained after crystallisation by cooling carries out cyclic electrolysis as electrolysis cathode liquid.
According to the method preparing lithium hydroxide of the present invention, the Mg/Li ratio in described salt lake brine with high magnesium-lithium ratio is 30 ~ 2000.
As preferably, the present invention, before preparing magnesium base functional materials, can dilute old halogen, make wherein Mg 2+for 0.5mol/L ~ 5mol/L.
According to the method preparing lithium hydroxide of the present invention, described step 2) soluble trivalent metal salt that adds is cation A l 3+, Fe 3+, Cr 3+, V 3+, Co 3+, Ga 3+or Ti 3+in one or both and negatively charged ion Cl -, CO 3 2-, NO 3-, F -, I -, SO 4 2-, ClO 3 -, OH -, H 2pO 4 -, WO 4 2-or one or both composition metal-salts in organic sulfonic acid root negatively charged ion.
According to the method preparing lithium hydroxide of the present invention, preferably, described step 2) soluble trivalent metal salt that adds is AlCl 36H 2o, CrCl 36H 2o or FeCl 36H 2one in O.
According to the method preparing lithium hydroxide of the present invention, preferably, step 3) described mixed ammonium/alkali solutions is the mixing solutions of sodium hydroxide and sodium carbonate.
According to the method preparing lithium hydroxide of the present invention, preferably, step 3) described coprecipitation method is pH static method.
According to the method preparing lithium hydroxide of the present invention, preferably, step 4) described drying temperature is 60 ~ 120 DEG C, time of drying is 6 ~ 48h.
Step 4 of the present invention) Mg/Li ratio in obtained low Mg/Li ratio mother liquor drops to 0.001 ~ 0.1.
According to the method preparing lithium hydroxide of the present invention, preferably, step 5) described adjustment low Mg/Li ratio mother liquor pH acid used is hydrochloric acid, nitric acid or sulfuric acid, the concentration of described acid is 0.5 ~ 3mol/L.
According to the method preparing lithium hydroxide of the present invention, preferably, step 6) to state effects of boron resin be one in LSC-800, D403, D564 or XSC-700.
According to the method preparing lithium hydroxide of the present invention, preferably, step 8) described elutriant be in hydrochloric acid or sulfuric acid one or both.
According to the method preparing lithium hydroxide of the present invention, step 13) concrete electrolysis mode can select electrolysis process well known in the art, preferably, step 13) described electrolytic process is: electrolyzer is made electrolytic groove, and current density is 1.0 ~ 3.0kA/m -2, average working voltage is at 2.8 ~ 3.5V, and cationic membrane is Eastern Mountain DF988, and chlorine and hydrogen reaction that electrolysis produces generate hydrochloric acid for step 5) or 7) pH value of middle regulator solution.
According to the method preparing lithium hydroxide of the present invention, preferably, described step 14) process be: the lithium hydroxide solution of nearly saturation concentration under agitation separates out lithium hydroxide solid through heating evaporation is concentrated, solidliquid mixture is cooled to 25 ~ 45 DEG C of crystallizations, vacuum filtration or centrifugation, obtain lithium hydroxide monohydrate, through the lithium hydroxide monohydrate product that washing, the content that obtains lithium hydroxide monohydrate 70 ~ 90 DEG C of dryings are greater than 99.0%.
It is (Mg+Ca)≤1ppm that boron ion, magnesium ion and calcium ion before the present invention also can utilize the ion exchange resin of magnesium, calcium to remove electrolysis in solution make to obtain impurity ion content in rich lithium-containing solution.
Reactive crystallization of the present invention generates purity >=99% of lithium hydroxide; The yield preparing lithium in lithium hydroxide process is 60% ~ 95%, and the yield of boron is 50% ~ 90%, and the utilization ratio of magnesium is for being greater than 99.98%.
The present invention with high magnesium lithium salts lake bittern water for raw material, add certain soluble trivalent metal salt, Mg/Li ratio in salt lake brine with high magnesium-lithium ratio is reduced by synthesizing magnesium-base layer-shaped functional materials, magnesium lithium in salt lake brine with high magnesium-lithium ratio is separated, the hydrotalcite mother liquor of low Mg/Li ratio is utilized to prepare lithium hydroxide afterwards, and by-product boric acid.Magnesium lithium provided by the invention is separated and the method for preparing lithium hydroxide effectively can not only solve previous methods complex process, cost is high, magnesium lithium separating effect is undesirable technical barrier, the cost preparing lithium hydroxide also greatly reduces, and the magnesium resource discarded is fully utilized reduce the cost of magnesium base functional materials simultaneously, there is good industrialization prospect.
The present invention compared with prior art has the following advantages:
(1) in the concentrated brine of salt lake, magnesium resource utilization ratio is low, waste resource, is even formed " magnesium evil ".The present invention makes full use of salt lake magnesium resource and has prepared the magnesium-base layer-shaped functional materials of high-quality, while reducing magnesium-base layer-shaped functional materials cost, for the comprehensive utilization of salt lake magnesium resource provides support.
(2) this invention greatly reduces the Mg/Li ratio in high magnesium lithium salts lake bittern water, low Mg/Li ratio salt lake brine is utilized to prepare high-purity hydrogen Lithium Oxide 98min, by-product boric acid simultaneously, what make magnesium in salt lake brine with high magnesium-lithium ratio, lithium, boron resource is able to high-valued and comprehensive development and utilization.
(3) present invention process is simple, is easy to control, and operational reliability is high, and the lithium hydroxide product purity obtained is high, and foreign matter content is low, can be directly used in the lithium source of lithium soap grease, battery industry and other lithium product, need not again purify.The rate of recovery of lithium is high, and cost compare is low, non-secondary pollution.
(4) present invention process is simple, easy to operate, water consumption and soda acid amount few, cost is low, improves economic benefit; Whole reaction process is nontoxic, harmless, pollution-free, and universality is strong.
Embodiment
Set forth the present invention further by the following examples, these embodiments are only presented for purposes of illustration, do not limit the scope of the invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition.
Embodiment 1
Get Qinghai East taigener salt-lake bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 1, and wherein Mg/Li ratio is 13.Get the old halogen of 1L, regulate wherein Mg 2+concentration be 5.5mol/L, add 175.6gAlCl 36H 2o is made into mixing salt solution; Take 700.4g sodium hydroxide, 116g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 11mol/L, adopts the precipitator method to synthesize magnesium aluminum-hydrotalcite when temperature 25 DEG C, pH are 8.The hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 50 DEG C of Water Under thermal aging 6h, by hydrotalcite product dry 6h under 60 DEG C of conditions, namely obtain magnesium aluminum-hydrotalcite product, product purity is 99%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.015.Adding 0.5mol/L hydrochloric acid regulates the pH of the hydrotalcite mother liquor obtained to be 7, to obtain hydrotalcite mother liquor with the flow velocity of 1mL/min by being equipped with the ion exchange column of LSC-800 resin, in the effluent liquid obtained, Boron contents is 10ppm, makes boron enrichment in ion exchange resin.With a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of hydrochloric acid washings with 1mL/min of 0.5mol/L by concentration, by the boron desorb in resin, desorption efficiency is 99.01%, obtains boron-rich mother liquor.Carry out forced evaporation-crystallisation by cooling to boron-rich mother liquor and obtain boric acid product, its purity is 99.12%, and the boron rate of recovery is 50%.
Add the pH that 0.5mol/L hydrochloric acid regulates the effluent liquid of above-mentioned acquisition, be neutral, remove the CO in solution simultaneously 3 2-.In solution, add calcium chloride, remove most SO 4 2-, then add bariumchloride, make SO 4 2-content drops to 50ppm.Afterwards forced evaporation is carried out to solution, make the massfraction enrichment of wherein lithium chloride reach 20%.Regulating the pH of rich lithium solution to be 3, with this solution for anolyte, take lithium hydroxide massfraction as the solution of 1% is catholyte, temperature be 50 DEG C, circular flow is 0.2L/min, current density is 1.0kA/m -2under condition, domestic ionic membrane and electrolyzer is selected to carry out electrolytic preparation lithium hydroxide, when lithium hydroxide concentration in catholyte stops electrolysis close to time saturated.Anticathode liquid carries out evaporation concentration and separates out lithium hydroxide solid, and solidliquid mixture is cooled to 25 DEG C, filtering separation can obtain lithium hydroxide monohydrate, and through washing, at 70 ~ 90 DEG C, drying obtains the lithium hydroxide monohydrate product that purity is 99.05%.Whole process lithium yield is 60%.
Table 1 embodiment bittern composition (unit: g/L)
Bittern title Mg 2+ Li + B 2O 3 Na + K + SO 4 2- Cl -
The old halogen of East Platform 85.47 6.75 15.77 10.42 7.69 29.58 251.60
Embodiment 2
Get Qinghai East taigener salt-lake bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 1, and wherein Mg/Li ratio is 12.Get the old halogen of 1L, regulate wherein Mg 2+concentration be 1.8mol/L, add 246gFeCl 36H 2o is made into mixing salt solution; Take 436g sodium hydroxide, 116g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 5.5mol/L, adopts pH static method to synthesize Mg-Fe ball when temperature 35 DEG C, pH are 9.The hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 60 DEG C of Water Under thermal aging 12h, by hydrotalcite product dry 12h under 70 DEG C of conditions, namely obtain Mg-Fe ball product, product purity is 99.2%, and the low Mg/Li ratio mother liquor Mg/Li ratio of acquisition is reduced to 0.008.Adding 1mol/L nitric acid regulates the pH of hydrotalcite mother liquor obtained to be 8, to the hydrotalcite mother liquor obtained with the flow velocity of 2mL/min by being equipped with the ion exchange column of D403 resin, in the effluent liquid obtained, Boron contents is 8ppm, makes boron enrichment in ion exchange resin.With a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of sulfuric acid scrubbing liquid with 2mL/min of 1.0mol/L by concentration, by the boron desorb in resin, desorption efficiency is 99.13%, obtains boron-rich mother liquor.Carry out forced evaporation-crystallisation by cooling to boron-rich mother liquor and obtain boric acid product, its purity is 99.03%, and the boron rate of recovery is 65%.
Add the pH that 1mol/L hydrochloric acid regulates the effluent liquid of above-mentioned acquisition, be neutral, remove the CO in solution simultaneously 3 2-, in solution, add calcium chloride, remove most SO 4 2-, then add bariumchloride, make SO 4 2-content drops to 45ppm.Afterwards forced evaporation is carried out to solution, make the massfraction enrichment of wherein lithium chloride reach 24%.Regulating the pH of rich lithium solution to be 2.5, with this solution for anolyte, take lithium hydroxide massfraction as the solution of 2% is catholyte, temperature be 60 DEG C, circular flow is 0.3L/min, current density is 1.5kA/m -2under condition, domestic ionic membrane and electrolyzer is selected to carry out electrolytic preparation lithium hydroxide, when lithium hydroxide concentration in catholyte stops electrolysis close to time saturated.Anticathode liquid carries out evaporation concentration and separates out lithium hydroxide solid, and solidliquid mixture is cooled to 30 DEG C, filtering separation can obtain lithium hydroxide monohydrate, and through washing, at 70 ~ 90 DEG C, drying obtains the lithium hydroxide monohydrate product that purity is 99.12%.Whole process lithium yield is 70%.
Embodiment 3
Get Qinghai Chaerhan salt lakes bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 2, and wherein Mg/Li ratio is 312.Get the old halogen of 1L, regulate wherein Mg 2+concentration be 1.58mol/L, add 421.6gCrCl 36H 2o is made into mixing salt solution; Take 569.6g sodium hydroxide, 150.8g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 4.75mol/L, adopts pH static method to synthesize magnesium chromium hydrotalcite when temperature 45 C, pH are 10.The hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 70 DEG C of Water Under thermal aging 18h, by hydrotalcite product dry 24h under 80 DEG C of conditions, namely obtain magnesium chromium hydrotalcite product, product purity is 99.13%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.006.Adding 1.5mol/L sulfuric acid regulates the pH of hydrotalcite mother liquor obtained to be 9, to the hydrotalcite mother liquor obtained with the flow velocity of 3mL/min by being equipped with the ion exchange column of D564 resin, in the effluent liquid obtained, Boron contents is 5ppm, makes boron enrichment in ion exchange resin.With a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of sulfuric acid scrubbing liquid with 3mL/min of 1.5mol/L by concentration, by the boron desorb in resin, desorption efficiency is 99.20%, obtains boron-rich mother liquor.Carry out forced evaporation-crystallisation by cooling to boron-rich mother liquor and obtain boric acid product, its purity is 99.09%, and the boron rate of recovery is 73%.
Add the pH that 1.5mol/L hydrochloric acid regulates the effluent liquid of above-mentioned acquisition, be neutral, remove the CO in solution simultaneously 3 2-, backward solution in add calcium chloride, remove most SO 4 2-, then add bariumchloride, make SO 4 2-content drops to 30ppm.Afterwards forced evaporation is carried out to solution, make the massfraction enrichment of wherein lithium chloride reach 26%.Regulating the pH of rich lithium solution to be 3.5, with this solution for anolyte, take lithium hydroxide massfraction as the solution of 2% is catholyte, temperature be 70 DEG C, circular flow is 0.4L/min, current density is 2.0kA/m -2under condition, domestic ionic membrane and electrolyzer is selected to carry out electrolytic preparation lithium hydroxide, when lithium hydroxide concentration in catholyte stops electrolysis close to time saturated.Anticathode liquid carries out evaporation concentration and separates out lithium hydroxide solid, and solidliquid mixture is cooled to 35 DEG C, filtering separation can obtain lithium hydroxide monohydrate, and through washing, at 70 ~ 90 DEG C, drying obtains the lithium hydroxide monohydrate product that purity is 99.03%.Whole process lithium yield is 80%.
Table 2 embodiment bittern composition (unit: g/L)
Bittern title Mg 2+ Li + Na + K + SO 4 2- Cl -
The old halogen of Cha Er Han 115.43 0.37 1.06 0.6224 11.83 331.46
Embodiment 4
Get Qinghai Chaerhan salt lakes bittern to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 2, and wherein Mg/Li ratio is 312.Get the old halogen of 1L, regulate wherein Mg 2+concentration be 1.19mol/L, add 531.6gAlCl 36H 2o is made into mixing salt solution; Take 569.6g sodium hydroxide, 150.8g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 3.56mol/L, adopts pH static method to synthesize magnesium aluminum-hydrotalcite when temperature 55 DEG C, pH are 11.The hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 80 DEG C of Water Under thermal aging 24h, by hydrotalcite product dry 36h under 90 DEG C of conditions, namely obtain magnesium aluminum-hydrotalcite product, product purity is 99.32%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.006.Adding 2mol/L hydrochloric acid regulates the pH of the hydrotalcite mother liquor obtained to be 10, to obtain hydrotalcite mother liquor with the flow velocity of 4mL/min by being equipped with the ion exchange column of XSC-700 resin, in the effluent liquid obtained, Boron contents is 9ppm, makes boron enrichment in ion exchange resin.With a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of hydrochloric acid washings with 4mL/min of 1.0mol/L by concentration, by the boron desorb in resin, desorption efficiency is 99.00%, obtains boron-rich mother liquor.Carry out forced evaporation-crystallisation by cooling to boron-rich mother liquor and obtain boric acid product, its purity is 99.25%, and the boron rate of recovery is 82%.
Add the pH that 2.5mol/L hydrochloric acid regulates the effluent liquid of above-mentioned acquisition, be neutral, remove the CO in solution simultaneously 3 2-, backward solution in add calcium chloride, remove most SO 4 2-, then add bariumchloride, make SO 4 2-content drops to 43ppm.Afterwards forced evaporation is carried out to solution, make the massfraction enrichment of wherein lithium chloride reach 28%.Regulating the pH of rich lithium solution to be 3, with this solution for anolyte, take lithium hydroxide massfraction as the solution of 3% is catholyte, temperature be 65 DEG C, circular flow is 0.5L/min, current density is 2.5kA/m -2under condition, domestic ionic membrane and electrolyzer is selected to carry out electrolytic preparation lithium hydroxide, when lithium hydroxide concentration in catholyte stops electrolysis close to time saturated.Anticathode liquid carries out evaporation concentration and separates out lithium hydroxide solid, and solidliquid mixture is cooled to 45 DEG C, filtering separation can obtain lithium hydroxide monohydrate, and through washing, at 70 ~ 90 DEG C, drying obtains the lithium hydroxide monohydrate product that purity is 99.14%.Whole process lithium yield is 90%.
Embodiment 5
Get Qinghai West Platform salt lake brine to evaporate after precipitated sodium chloride, potassium magnesium mixed salt through salt pan, the old halogen composition obtained is in table 3, and wherein Mg/Li ratio is 56.Get the old halogen of 1L, regulate wherein Mg 2+concentration be 0.79mol/L, add 1047.2gCrCl 36H 2o is made into mixing salt solution; Take 471.6g sodium hydroxide, 124.8g sodium carbonate configuration sodium hydroxide volumetric molar concentration is the mixed ammonium/alkali solutions of 2.36mol/L, adopt pH static method to synthesize magnesium chromium hydrotalcite when temperature 70 C, pH are 12, the hydrotalcite slurry of preparation carries out filtration washing to filtrate weakly acidic pH at 150 DEG C of Water Under thermal aging 48h.By hydrotalcite product dry 48h under 120 DEG C of conditions, namely obtain magnesium chromium hydrotalcite product, product purity is 99.53%, and in the low Mg/Li ratio mother liquor of acquisition, Mg/Li ratio is reduced to 0.003.Adding 3mol/L nitric acid regulates the pH of the hydrotalcite mother liquor obtained to be 8, to obtain hydrotalcite mother liquor with the flow velocity of 5mL/min by being equipped with the ion exchange column of LSC-800 resin, in the effluent liquid obtained, Boron contents is 5ppm, makes boron enrichment in ion exchange resin.With a certain amount of distilled water wash ion exchange column, removing residual mother liquor, be the flow velocity eluent ion exchange column of hydrochloric acid washings with 5mL/min of 0.5mol/L afterwards by concentration, by the boron desorb in resin, desorption efficiency is 99.18%, obtains boron-rich mother liquor.Carry out forced evaporation-crystallisation by cooling to boron-rich mother liquor and obtain boric acid product, its purity is 99.06%, and the boron rate of recovery is 90%.
Add the pH that 3.0mol/L hydrochloric acid regulates the effluent liquid of above-mentioned acquisition, be neutral, remove the CO in solution simultaneously 3 2-, in solution, add calcium chloride, remove most SO 4 2-, then add bariumchloride, make SO 4 2-content drops to 38ppm.Afterwards forced evaporation is carried out to solution, make the massfraction enrichment of wherein lithium chloride reach 30%.Regulating the pH of rich lithium solution to be 3, with this solution for anolyte, take lithium hydroxide massfraction as the solution of 3% is catholyte, temperature be 55 DEG C, circular flow is 0.3L/min, current density is 3.0kA/m -2under condition, domestic ionic membrane and electrolyzer is selected to carry out electrolytic preparation lithium hydroxide, when lithium hydroxide concentration in catholyte stops electrolysis close to time saturated.Anticathode liquid carries out evaporation concentration and separates out lithium hydroxide solid, and solidliquid mixture is cooled to 40 DEG C, filtering separation can obtain lithium hydroxide monohydrate, and through washing, at 70 ~ 90 DEG C, drying obtains the lithium hydroxide monohydrate product that purity is 99.35%.Whole process lithium yield is 95%.
Table 3 embodiment bittern composition (unit: g/L)
Bittern title Mg 2+ Li + Na + K + SO 4 2- Cl -
The old halogen of West Platform 96.56 1.71 5.87 1.19 12.79 291.12
Certainly; the present invention can also have various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art can openly make various corresponding change and distortion according to of the present invention, but these change accordingly and are out of shape the protection domain that all should belong to claim of the present invention.

Claims (9)

1. utilize salt lake brine with high magnesium-lithium ratio to prepare a method for lithium hydroxide, comprise the following steps:
1) according to Phase Diagram for Aqueous Salt Solutions principle, multistage evaporation is carried out with concentrated salt lake brine to salt lake brine, and reduce Mg/Li ratio by separating out salt, after evaporative crystallization, obtain the old halogen that Mg/Li ratio is 10 ~ 500;
2) Mg in old halogen is regulated 2+concentration, make Mg 2+concentration, at 0.5mol/L ~ 5mol/L, adds soluble trivalent metal salt and is made into mixing salt solution; Wherein, described Mg 2+be 1 ~ 5 with the cationic mol ratio of trivalent metal salt;
3) to step 2) mixing salt solution in add mixed ammonium/alkali solutions, OH in mixed ammonium/alkali solutions -volumetric molar concentration is Mg 2+2 ~ 3 times of volumetric molar concentration, adopt coprecipitation method to carry out into nuclear reaction under temperature is 25 ~ 70 DEG C of conditions, carry out ageing after nucleation, Aging Temperature 50 ~ 150 DEG C, digestion time is 6 ~ 48h;
4) by step 3) mixed liquor after ageing after filtration, washing and dry, obtain magnesium based hydrotalcite and low Mg/Li ratio mother liquor;
5) to step 4) low Mg/Li ratio mother liquor in add acid, adjust ph is 7 ~ 10;
6) by the mother liquor after adjust ph with the ion exchange column by being equipped with effects of boron resin of the flow velocity of 1 ~ 5mL/min, make boron enrichment in the ion exchange column that effects of boron resin is housed, to make in effluent liquid Boron contents at below 10ppm;
7) use distilled water wash ion exchange column, until not chloride ion-containing in flow liquid, removing residual mother liquor also obtains effluent liquid;
8) by concentration be the flow velocity eluent ion exchange column of elutriant with 1 ~ 5mL/min of 0.5 ~ 1.5mol/L, by the boron desorb in effects of boron resin, make the desorption efficiency of boron more than 99%, obtain boron-rich mother liquor;
9) multistage evaporation is carried out to boron-rich mother liquor or forced evaporation concentrates, crystallisation by cooling is carried out to the mother liquor after concentrated, obtained boric acid;
10) to above-mentioned steps 7) in add 0.5 ~ 3mol/L hydrochloric acid in effluent liquid, regulate the pH value of effluent liquid, be neutral, remove the CO in solution simultaneously 3 2-;
11) removing step 10) in SO in effluent liquid after adjust ph 4 2-, make SO 4 2-content is not higher than 50ppm;
12) carry out the evaporation of multistage salt pan or forced evaporation to above-mentioned solution, obtaining lithium chloride mass concentration is 20% ~ 30% rich lithium solution;
13) using rich lithium solution as anolyte, be that the lithium hydroxide solution of 1% ~ 3% is as catholyte using massfraction, be that 0.2 ~ 0.5L/min carries out electrolysis at temperature 50 ~ 70 DEG C, circular flow, obtained the lithium hydroxide monohydrate solution of nearly saturation concentration by cationic membrane at cathode compartment;
14) by step 13) the lithium hydroxide monohydrate solution of nearly saturation concentration that obtains is dry through evaporation concentration, crystallisation by cooling, washing, obtains lithium hydroxide monohydrate.
2. the method preparing lithium hydroxide according to claim 1, is characterized in that, the Mg/Li ratio in described salt lake brine with high magnesium-lithium ratio is 30 ~ 2000.
3. the method preparing lithium hydroxide according to claim 1, is characterized in that, described step 2) soluble trivalent metal salt that adds is cation A l 3+, Fe 3+, Cr 3+, V 3+, Co 3+, Ga 3+or Ti 3+in one or both and negatively charged ion Cl -, CO 3 2-, NO 3-, F -, I -, SO 4 2-, ClO 3 -, OH -, H 2pO 4 -, WO 4 2-or one or both composition metal-salts in organic sulfonic acid root negatively charged ion.
4. the method for standby lithium hydroxide according to claim 3, is characterized in that, described step 2) soluble trivalent metal salt that adds is AlCl 36H 2o, CrCl 36H 2o or FeCl 36H 2one in O.
5. the method preparing lithium hydroxide according to claim 1, is characterized in that, step 3) described mixed ammonium/alkali solutions is the mixing solutions of sodium hydroxide and sodium carbonate, CO in mixing solutions 3 2-and OH -molar concentration rate is 1:10 ~ 1:16.
6. the method preparing lithium hydroxide according to claim 1, is characterized in that, step 3) described coprecipitation method is pH static method, pH is between 8 ~ 12.
7. the method preparing lithium hydroxide according to claim 1, is characterized in that, step 5) described adjustment low Mg/Li ratio mother liquor pH acid used is hydrochloric acid, nitric acid or sulfuric acid, the concentration of described acid is 0.5 ~ 3mol/L.
8. the method preparing lithium hydroxide according to claim 1, is characterized in that, step 6) described effects of boron resin is one in LSC-800, D403, D564 or XSC-700.
9. the method preparing lithium hydroxide according to claim 1, is characterized in that, step 13) pH value of adjustment anolyte is 2.5 ~ 3.5 before electrolysis.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107164777A (en) * 2017-05-12 2017-09-15 中国科学院过程工程研究所 A kind of method of film electrolysis separating magnesium and enriching lithium from salt lake brine with high magnesium-lithium ratio
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
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1579937A (en) * 2003-07-31 2005-02-16 北京化工大学 Method for preparing nano-level magnesium-aluminium hydrotalcite using bittern as raw material
CN101538057A (en) * 2009-04-24 2009-09-23 钟辉 Method for separating magnesium from lithium and extracting lithium from brine
CN103924258A (en) * 2014-04-28 2014-07-16 中国科学院青海盐湖研究所 Method for preparing lithium hydroxide through electrolysis of salt lake brine
CN104357677A (en) * 2014-11-26 2015-02-18 中国科学院青海盐湖研究所 Method for extracting lithium from salt lake brine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1579937A (en) * 2003-07-31 2005-02-16 北京化工大学 Method for preparing nano-level magnesium-aluminium hydrotalcite using bittern as raw material
CN101538057A (en) * 2009-04-24 2009-09-23 钟辉 Method for separating magnesium from lithium and extracting lithium from brine
CN103924258A (en) * 2014-04-28 2014-07-16 中国科学院青海盐湖研究所 Method for preparing lithium hydroxide through electrolysis of salt lake brine
CN104357677A (en) * 2014-11-26 2015-02-18 中国科学院青海盐湖研究所 Method for extracting lithium from salt lake brine

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107164777A (en) * 2017-05-12 2017-09-15 中国科学院过程工程研究所 A kind of method of film electrolysis separating magnesium and enriching lithium from salt lake brine with high magnesium-lithium ratio
CN107164777B (en) * 2017-05-12 2019-01-25 中国科学院过程工程研究所 A kind of method of film electrolysis separating magnesium and enriching lithium from salt lake brine with high magnesium-lithium ratio
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
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

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