CN104803399A - Method for preparing high-purity magnesium oxalate, lithium carbonate and high-purity nanometer magnesia from salt lake brine of high magnesium-lithium ratio - Google Patents
Method for preparing high-purity magnesium oxalate, lithium carbonate and high-purity nanometer magnesia from salt lake brine of high magnesium-lithium ratio Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity magnesium oxalate and lithium carbonate from salt lake brine of high magnesium-lithium ratio. The method comprises the following steps: 1) filtering the salt lake brine to remove suspended matters and solid impurities; 2) adding oxalic acid into the filtered salt lake brine; carrying out reaction for 30 to 180 min under the conditions that the temperature is 20 to 60 DEG C, the pH is 3 to 5, and the stirring speed is 150 to 500 rpm, so as to obtain brine of low magnesium-lithium ratio and magnesium oxalate precipitate; washing the magnesium oxalate precipitate with 40 to 60 DEG C hot water for 3 to 5 times; drying the washed magnesium oxalate precipitate at 80 to 102 DEG C for 60 to 120 min to obtain the high-purity magnesium oxalate of which the purity is larger than or equal to 98%; 3) adding an impurity removing agent into the brine of low magnesium-lithium ratio, so as to obtain refined brine; adding sodium carbonate into the refined brine to obtain lithium carbonate crystal; filtering the lithium carbonate crystal; carrying out washing and drying to obtain lithium carbonate. The magnesium oxalate prepared according to the method is high in purity.
Description
Technical field
The invention belongs to salt lake brine comprehensive utilization of resources field, particularly relate to a kind of method of high purity magnesium oxalate, Quilonum Retard and high-purity nano magnesia from salt lake brine with high magnesium-lithium ratio.
Background technology
Along with the lithium energy, lithium alloy, the application of lithiumation chemical product in the industries such as communication, electromobile, electric power, aerospace, refrigeration, medicine are extensively more next, increasing to the demand of industrial lithium carbonate on market.
The industrial resource for extracting lithium mainly contains two classes, and a class is containing lithium solid mineral, and another kind of is various containing lithium salts lake.Wherein, in salt lake, lithium accounts for about 70% of world's lithium resource reserves, simultaneously due to the salt lake in some areas in the world, as the Yin Feng lake etc. of the Ah tower Karma playa lake of South America Chile, the Uyuni salt lake of Bolivia, Argentine father-in-law's mine-laying Mu Aiertuo, the U.S., be low Mg/Li ratio (Mg/Li < 10) bittern, extract Quilonum Retard technique simple, cost is low, and the lithium extracted from these salt lakes at present accounts for about 80% of world market.
Also be richly stored with lithium resource in the Caidamu Basin in China Qinghai and the salt lake of Tibet region, but most of salt lake as Yi Liping, the Dong Ji in Qinghai like this, salt lake like this, Xiji, the E Ya in Tibet arranges, Qazz is high Mg/Li ratio magnesium sulfate bittern (Mg/Li=20 ~ 90) according to salt lake etc., carry that lithium difficulty is large, production cost is high, cause the lithium carbonate product produced commercially to be lacked competitiveness.
In order to solve, separating magnesium lithium technical difficulty from salt lake brine with high magnesium-lithium ratio is large, cost is in problem not, studies for a long period of time both at home and abroad, develops the technique that following several large class salt lake brine carries lithium:
(1) precipitator method.The precipitation agent adopted is one or more in sodium carbonate, bicarbonate of ammonia, ammonia, calcium hydroxide, sodium hydroxide or aluminate.In precipitation agent and bittern, magnesium ion generates magnesiumcarbonate, magnesium hydroxide or boron magnesium, the co-precipitation of aluminium lithium, realizes magnesium lithium and is separated.Because great majority are precipitated as jelly, filter, washing is very difficult, cause and carry secretly serious and energy consumption is high.The chemical reagent that heavy magnesium consumption is a large amount of, the throw out obtained, but because foreign matter content is high, utility value is low, causes the cost producing Quilonum Retard very high.Therefore except the sodium carbonate precipitator method are used for from low Mg/Li ratio bittern except separating magnesium, all the other all fail to realize suitability for industrialized production.
(2) solvent extration.Solvent extration utilizes the lithium in some organic solvent extraction bittern, and extraction agent mainly contains: phosphorous organic extractant, amine extractant, diketone class, fatty alcohol, ether extration agent etc.The applied research that solvent extration carries lithium in bittern is decades-long, but because of the molten damage of extraction agent large, comparatively serious to equipment corrosion, fail to realize suitability for industrialized production to reasons such as the pollution of environment are large always.
(3) ion-exchange and absorption method.Ion-exchange and absorption method adopt unformed oxyhydroxide sorbent material, ion-sieve type sorbent material, metaantimmonic acid salt form sorbent material, aluminate type sorbent material from bittern, to adsorb lithium ion, then eluted from sorbent material by lithium ion, realizes the separation of lithium.But at present because ion-exchange, sorbent material manufacturing cost are higher, or because loading capacity is large compared with low, molten damage, cycle index is few, granulations is difficult, is still in the experimental study stage, do not obtain industrial application breakthrough.
(4) leaching method is calcined.Calcining leaching method is that old halogen evaporate the four aqueous magnesium chloride solids obtained, and at 700 DEG C, calcine 2h obtain magnesium oxide, magnesium oxide goes out to obtain lithium-containing solution with water logging again, the impurity then in removing solution, evaporation concentration, adds sodium carbonate and is settled out Quilonum Retard.Qinghai company limited of CITIC Guoan adopts calcining leaching method to establish the full scale plant of a set of annual output 5000 tons of Quilonum Retards.But because this process energy consumption is high, serious to equipment corrosion, cause the production cost of product high, commercially lack competitiveness.
(5) electroosmose process.Bittern, by one or more levels electrodialyzer, utilizes monovalent cation selective ion exchange membrane and univalent anion selective ion exchange membrane alternate operation to realize the concentrated of lithium ion.The rich lithium bittern obtained, then carry out deep impurity-removing, concentrated, the obtained Quilonum Retard of precipitation.Electroosmose process effectively can realize magnesium lithium and be separated, but because power consumption is high and produce poisonous chlorine and explosive hydrogen, production cost is higher and danger is larger.
(6) Nanofiltering membrane.Nanofiltration membrane is a kind of new membrane parting material being widely used in purifying water process, utilizes film to the rejection effect difference of different valence state ion, realizes retaining divalence and polyvalent ion more than 90%, few to retaining of monovalent ion, thus realizes the separation of magnesium lithium.The application that current Nanofiltering membrane is carried in lithium at salt lake brine is in the starting stage, there is many limitation and incomplete place, also has longer distance from industrial applications.
It is that production cost is high that current China extracts the subject matter existed containing lithium product from salt lake brine with high magnesium-lithium ratio, cannot compete with external product, the major cause that cost is high is because the Mg/Li ratio in bittern is high, separating difficulty is large, and current put forward lithium complex process, tediously long, energy consumption is high, magnesium composition after magnesium lithium is separated is complicated, magnesium ion in major part technique and other metal ion co-precipitation can not be produced high-purity magnesium oxide and can not be obtained nano magnesia, the magnesium salts that minority explained hereafter goes out also is primary products, be processed into high-purity or nano level magnesium products, need a large amount of chemical through multiple tracks purification process and consumption and the energy, therefore tooling cost is very high.
Be not difficult to find out from the Summary on technology of the salt lake brine separating magnesium lithium studied both at home and abroad above, enriching lithium, sepn process energy consumption is high, all ingredients, high material consumption, isolated magnesium products economic worth is low, cost is high, and large to the pollution of environment, be that restriction China salt lake brine with high magnesium-lithium ratio is carried lithium and realized industrialized major obstacle.
Therefore if resolve the problems referred to above, just can realize China's salt lake brine and propose the scale operation of lithium and produce good economic benefit.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of method of high purity magnesium oxalate, Quilonum Retard and high-purity nano magnesia from salt lake brine with high magnesium-lithium ratio.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
From salt lake brine with high magnesium-lithium ratio, produce a method for magnesium oxalate and Quilonum Retard, comprise the following steps:
1) suspended substance filtered in salt lake brine and solid impurity is crossed;
2) in step 1) after salt lake brine in add oxalic acid, temperature be 20 ~ 60 DEG C, pH=3 ~ 5, stirring velocity be the condition of 150 ~ 500rpm under reaction 30 ~ 180min, react rear filtration and has obtained low Mg/Li ratio bittern and magnesium oxalate precipitates;
Precipitate 3 ~ 5 times with magnesium oxalate described in 40 ~ 60 DEG C of hot washes, at 80 ~ 102 DEG C, dry 60 ~ 120min obtains the high-purity oxalic acid magnesium of purity >=98%;
3) in step 2) add cleaner in the low Mg/Li ratio bittern that obtains, obtain refining bittern, in described refining bittern, add sodium carbonate obtain Quilonum Retard crystal, described Quilonum Retard crystal is filtered, washs, drying obtains Quilonum Retard.
Above-mentioned method, preferably, in the oxalic acid added and salt lake brine, the mol ratio of magnesium ion is 1 ~ 1.3.
Above-mentioned method, preferably, described step 2) in, pH controls by adding sodium hydroxide.
Above-mentioned method, preferably, described step 3) in, cleaner is one or more in sodium carbonate, volatile salt, ammoniacal liquor, lime, milk of lime, sodium hydroxide, calcium chloride, bariumchloride; Temperature in dedoping step is 10 ~ 40 DEG C, and stirring velocity is 300 ~ 600rpm, and the reaction times is 30 ~ 120min.
Above-mentioned method, preferably, described step 1) in, described salt lake brine is separated out after potassium mixed salt by magnesium sulfate bittern through evaporation, begins to enter the bittern in precipitation bischofite stage or the old halogen after separating out bischofite.
Above-mentioned method, preferably, described step 1) in, described salt lake brine is by the old halogen formed after chloride type bittern evaporation.
Above-mentioned method, preferably, described step 1) in, the filtration unit that the suspended substance in filter salts lake bittern water and solid impurity adopt is the one or more combination in millipore filter, kieselguhr filter, sand-bed filter, plate-and-frame filter press, activated charcoal filter.
As a total inventive concept, the present invention also provides a kind of method of high purity nano magnesia, and the high-purity oxalic acid magnesium prepared with aforesaid method is raw material, obtains high-purity nano magnesia by thermal degradation.
Above-mentioned method, preferably, the detailed process of described high purity nano magnesia is: magnesium oxalate is placed in control climate stove, in 450 ~ 900 DEG C of temperature range, heat 4 ~ 6h, namely prepare that particle diameter is 10nm ~ 30nm, purity be not less than 98% high-purity nano magnesia.
Compared with prior art, the invention has the advantages that:
1) the present invention is by strictly controlling deposition condition, particularly pH value is strict controlled in the scope of 3 ~ 5, the magnesium oxalate that purity is very high is settled out from salt lake brine, other compositions are as very low in lithium oxalate, potassium oxalate, sodium oxalate etc., by the impurity of hot wash mechanical entrapment, high-purity oxalic acid magnesium can be obtained.The cheap chemical product of industrial scale operation is converted into high-purity oxalic acid magnesium (purity >=98%), and technique is simple and direct, and operation is easy to control, and low equipment investment, process energy consumption is low, environmentally safe.
2) the present invention sinks the low Mg/Li ratio bittern obtained after magnesium, and magnesium lithium separating effect is better.
3) the high-purity oxalic acid magnesium produced of the present invention commercially except direct marketing, as the further deep processing of high quality raw material, can also be produced the high-purity nano magnesia material that added value is higher, significantly improves the economic benefit of production except as product.Putting forward the overall economic efficiency of lithium by improving salt lake brine, significantly can strengthen lithium carbonate product competitive power commercially.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Apart from special instruction, all ingredients used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
Embodiment 1:
A method for high purity magnesium oxalate and Quilonum Retard from salt lake brine with high magnesium-lithium ratio of the present invention, comprises the following steps:
1) start after separating out potassium mixed salt according to certain salt lake magnesium sulfate bittern evaporation to enter the bittern composition of separating out the bischofite stage, adopt industrial KCl, NaCl, MgSO
4, MgCl
2carry out composite bittern composition (wt, %) obtained in table 1.
The composition of table 1 salt lake brine
| K + | Na + | Mg 2+ | Li + | Ca 2+ | Cl - | SO 4 2- | Mg/Li |
| 0.06 | 0.13 | 8.83 | 0.23 | 0.002 | 24.64 | 2.68 | 38.39 |
Get salt lake brine (brine densities d=1.328,20 DEG C, the pH=4.6) 1000ml of above-mentioned composition, adopt the solid sundries in millipore filter removing bittern and suspended substance.
2) adopt clean fresh water by step 1) after salt lake brine dilute 1 times after, (add-on of oxalic acid makes the magnesium ion in bittern all be precipitated as 115% of the theoretical amount of magnesium oxalate to add industrial solid oxalic acid (purity is 99.6%) 701.75g while stirring, namely in the add-on of oxalic acid and bittern, the mol ratio of magnesium ion is 1.15:1), the speed stirred is 200rpm, 4M sodium hydroxide solution is dripped in the process stirred, regulate pH close to 4.0, temperature of reaction is 20 ~ 23 DEG C, reaction times is 60min, reaction terminates rear suction filtration and obtains low Mg/Li ratio salt lake brine (Mg/Li ratio=4.26) and magnesium oxalate precipitation.The hot wash 4 times of 45 DEG C of magnesium oxalate precipitation, at 85 DEG C, drying obtains the high-purity oxalic acid magnesium 626.79g that purity is 99.45% for 90 minutes, and the magnesium rate of recovery reaches 90.69%.
3) to step 2) the low Mg/Li ratio salt lake brine that obtains adds milk of lime (add-on of milk of lime is 103% of the theoretical amount that the sulfate radical in bittern and oxalate are precipitated completely) while stirring, temperature 15 ~ 20 DEG C, stirring velocity is 400rpm, time is 60min, clarification, filtration.
Saturated sodium carbonate solution (add-on of sodium carbonate solution is 105% of the theoretical amount that the magnesium ion in bittern is precipitated completely) is added while stirring again in bittern after filtration, stirring velocity is 400rpm, time is 30min, leave standstill, filter, obtain refining bittern, after refining, bittern adds sodium carbonate by known method, stirring reaction, crystallization, filtration, dry obtained Quilonum Retard.
Get step 2) the magnesium oxalate 200g for preparing, be placed in roasting 5h at 600 DEG C, control climate stove, obtain high-purity nano magnesia 57.78g, MgO purity is 99.39% after testing, and mean particle size is 21nm.The magnesium rate of recovery 99.49%.
Embodiment 2:
The method producing magnesium oxalate and Quilonum Retard from salt lake brine with high magnesium-lithium ratio of the present invention, comprises the following steps:
1) separate out the old halogen composition after bischofite according to certain salt lake magnesium sulfate bittern evaporation, adopt industrial KCl, NaCl, MgSO
4, MgCl
2carry out composite bittern composition (wt, %) obtained in table 2.
The composition of table 2 salt lake brine
| K + | Na + | Mg 2+ | Li + | Ca 2+ | Cl - | SO 4 2- | Mg/Li |
| 0.05 | 0.11 | 8.39 | 0.41 | 0.001 | 24.36 | 2.61 | 20.46 |
Get above-mentioned composition bittern (brine densities d=1.341,20 DEG C, bittern pH=4.5) 1000ml, adopt the solid sundries in kieselguhr filter removing bittern and suspended substance.
2) adopt clean fresh water by step 1) after salt lake brine dilute 3 times after, (add-on of oxalic acid makes the magnesium ion in bittern all be precipitated as 120% of the theoretical amount of magnesium oxalate to add industrial solid oxalic acid (purity is 99.6%) 702.58g while stirring, namely in the add-on of oxalic acid and bittern, the mol ratio of magnesium ion is 1.2:1), the speed stirred is 300rpm, 3M sodium hydroxide solution is dripped in the process stirred, regulate pH close to 4.0, temperature of reaction is 30 ~ 32 DEG C, reaction times is 90min, reaction terminates rear suction filtration and obtains low Mg/Li ratio salt lake brine (Mg/Li ratio=2.14) and magnesium oxalate precipitation.The hot wash 5 times of 50 DEG C of magnesium oxalate precipitation, at 95 DEG C, drying obtains the magnesium oxalate 605.34g that purity is 99.75% for 60 minutes, and the magnesium rate of recovery reaches 90.79%.
3) to step 2) the low Mg/Li ratio salt lake brine that obtains adds milk of lime while stirring, (add-on of milk of lime is 102% of the theoretical amount that the sulfate radical in bittern and oxalate are precipitated completely), temperature is 25 ~ 30 DEG C, stirring velocity is 400rpm, time is 60min, clarification, filtration.
Saturated sodium carbonate solution (add-on of sodium carbonate solution is 105% of the theoretical amount that the magnesium ion in bittern is precipitated completely) is added while stirring again in bittern after filtration, stirring velocity is 400rpm, time is 30min, leave standstill, filter, obtain refining bittern, after refining, bittern adds sodium carbonate by known method, stirring reaction, crystallization, filtration, dry obtained Quilonum Retard.
Get step 2) the magnesium oxalate 200g for preparing, be placed in roasting 5h at 580 DEG C, control climate stove, obtain high-purity nano magnesia 56.74g, MgO purity is 99.62% after testing, and mean particle size is 17nm.The magnesium rate of recovery 99.31%.
Embodiment 3:
A method for high purity magnesium oxalate and Quilonum Retard from salt lake brine with high magnesium-lithium ratio of the present invention, comprises the following steps:
1) after analysing potassium according to certain chloride type bittern evaporation, old halogen composition, adopts industrial KCl, NaCl, MgCl
2, CaCl
2, MgSO
4carry out composite bittern composition (wt, %) obtained in table 3.
The composition of table 3 salt lake brine
| K + | Na + | Mg 2+ | Li + | Ca 2+ | Cl - | SO 4 2- | Mg/Li |
| 0.17 | 0.06 | 8.44 | 0.05 | 0.09 | 25.12 | 0.02 | 164.8 |
Get salt lake brine (brine densities d=1.337,20 DEG C, the pH=4.2) 1000ml of above-mentioned composition, adopt the solid sundries in activated charcoal filter removing bittern and suspended substance.
2) adopt clean fresh water by step 1) after salt lake brine dilute 2 times after, (add-on of oxalic acid makes the magnesium ion in bittern all be precipitated as 125% of the theoretical amount of magnesium oxalate to add industrial solid oxalic acid (purity is 99.6%) 734.02g while stirring, namely in the add-on of oxalic acid and bittern, the mol ratio of magnesium ion is 1.25:1), the speed stirred is 250rpm, 4M sodium hydroxide solution is dripped in the process stirred, regulate pH close to 4.0, temperature of reaction is 35 ~ 38 DEG C, reaction times is 60min, reaction terminates rear suction filtration and obtains low Mg/Li ratio salt lake brine (Mg/Li ratio=17.05) and magnesium oxalate precipitation.The hot wash 3 times of 50 DEG C of magnesium oxalate precipitation, at 100 DEG C, drying obtains the magnesium oxalate 592.67g that purity is 98.13% for 60 minutes, and the magnesium rate of recovery reaches 91.21%.
3) to step 2) the low Mg/Li ratio salt lake brine that obtains adds milk of lime (add-on of milk of lime is 102% of the theoretical amount that the sulfate radical in bittern and oxalate are precipitated completely) while stirring, temperature 30 ~ 35 DEG C, stirring velocity is 450rpm, time is 45min, clarification, filtration.
Saturated sodium carbonate solution (add-on of sodium carbonate solution is 105% of the theoretical amount that the magnesium ion in bittern is precipitated completely) is added while stirring again in bittern after filtration, stirring velocity is 350rpm, time is 30min, leave standstill, filter, obtain refining bittern, after refining, bittern adds sodium carbonate by known method, stirring reaction, crystallization, filtration, dry obtained Quilonum Retard.
Get step 2) the magnesium oxalate 200g for preparing, be placed in roasting 4h at 680 DEG C, control climate stove, obtain high-purity nano magnesia 60.27g, MgO purity is 98.22% after testing, and mean particle size is 27nm.The magnesium rate of recovery 99.26%.
Claims (9)
1. the method for high purity magnesium oxalate and Quilonum Retard from salt lake brine with high magnesium-lithium ratio, is characterized in that, comprise the following steps:
1) suspended substance filtered in salt lake brine and solid impurity is crossed;
2) in step 1) after salt lake brine in add oxalic acid, temperature be 20 ~ 60 DEG C, pH=3 ~ 5, stirring velocity be the condition of 150 ~ 500rpm under reaction 30 ~ 180min, react rear filtration and has obtained low Mg/Li ratio bittern and magnesium oxalate precipitates;
Precipitate 3 ~ 5 times with magnesium oxalate described in 40 ~ 60 DEG C of hot washes, at 80 ~ 102 DEG C, dry 60 ~ 120min obtains the high-purity oxalic acid magnesium of purity >=98%;
3) in step 2) add cleaner in the low Mg/Li ratio bittern that obtains, obtain refining bittern, in described refining bittern, add sodium carbonate obtain Quilonum Retard crystal, described Quilonum Retard crystal is filtered, washs, drying obtains Quilonum Retard.
2. the method for claim 1, is characterized in that, described step 2) in, in the oxalic acid added and salt lake brine, the mol ratio of magnesium ion is 1 ~ 1.3.
3. the method for claim 1, is characterized in that, described step 2) in, pH controls by adding sodium hydroxide.
4. method as claimed in claim 1, is characterized in that, described step 3) in, cleaner is one or more in sodium carbonate, volatile salt, ammoniacal liquor, lime, milk of lime, sodium hydroxide, calcium chloride, bariumchloride; Temperature in dedoping step is 10 ~ 40 DEG C, and stirring velocity is 300 ~ 600rpm, and the reaction times is 30 ~ 120min.
5. the method as described in any one of Claims 1 to 4, it is characterized in that, described step 1) in, described salt lake brine is separated out after potassium mixed salt by magnesium sulfate bittern through evaporation, begins to enter the bittern in precipitation bischofite stage or the old halogen after separating out bischofite.
6. the method as described in any one of Claims 1 to 4, is characterized in that, described step 1) in, described salt lake brine is by the old halogen formed after chloride type bittern evaporation.
7. the method as described in any one of Claims 1 to 4, it is characterized in that, described step 1) in, the filtration unit that the suspended substance in filter salts lake bittern water and solid impurity adopt is the one or more combination in millipore filter, kieselguhr filter, sand-bed filter, plate-and-frame filter press, activated charcoal filter.
8. a method for high purity nano magnesia, is characterized in that, the high-purity oxalic acid magnesium prepared with the method described in any one of claim 1 ~ 7, for raw material, obtains high-purity nano magnesia by thermal degradation.
9. method as claimed in claim 8, it is characterized in that, the detailed process of described high purity nano magnesia is: magnesium oxalate is placed in control climate stove, in 450 ~ 900 DEG C of temperature range, heat 4 ~ 6h, namely prepare that particle diameter is 10nm ~ 30nm, purity be not less than 98% high-purity nano magnesia.
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| CN108217701A (en) * | 2018-04-11 | 2018-06-29 | 宜春市鼎鑫高能科技有限公司 | A kind of lithium carbonate process units |
| CN109825717A (en) * | 2019-04-02 | 2019-05-31 | 武汉科技大学 | A method of recycling magnesium, iron and aluminium step by step from containing vanadium solution |
| CN110357055A (en) * | 2019-08-09 | 2019-10-22 | 深圳市德方纳米科技股份有限公司 | A kind of method and application thereof extracted lithium from salt lake bittern and prepare lithium phosphate |
| CN110357055B (en) * | 2019-08-09 | 2022-07-15 | 深圳市德方纳米科技股份有限公司 | Method for extracting lithium from salt lake brine and preparing lithium phosphate and application thereof |
| CN112897557A (en) * | 2021-02-07 | 2021-06-04 | 湖南永杉锂业有限公司 | Process for preparing high-purity lithium carbonate from lithium salt solution |
| CN114031090A (en) * | 2021-11-18 | 2022-02-11 | 中山市清融嘉创能源科技有限责任公司 | Method for preparing beta-spodumene from brine with high magnesium-lithium ratio |
| CN114031090B (en) * | 2021-11-18 | 2023-07-18 | 中山市清融嘉创能源科技有限责任公司 | Method for preparing beta-spodumene from brine with high magnesium-lithium ratio |
| CN114671492A (en) * | 2022-03-09 | 2022-06-28 | 大连理工大学 | Bipolar membrane system for efficiently removing magnesium ions in salt lake brine in-situ alkali preparation |
| CN114671492B (en) * | 2022-03-09 | 2023-08-18 | 大连理工大学 | Bipolar membrane system for efficiently removing magnesium ions in salt lake brine by in-situ alkali preparation |
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