CA2822196A1 - Dust-free grade lithium hydroxide monohydrate and its preparation method - Google Patents
Dust-free grade lithium hydroxide monohydrate and its preparation method Download PDFInfo
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Abstract
Provided are a dust free lithium hydroxide monohydrate and a preparation method therefor, which belong to the technical field of preparation of lithium hydroxide. The technical problem to be solved is to provide a dust-free non-hardening lithium hydroxide monohydrate LiOHH2O in view of the problems of hardening of wet LiOHH2O and dusting of dry LiOHH2O existing in the prior art. The lithium hydroxide monohydrate is a wet loose granular product, wherein the moisture content is lower than or equal to 3.5%, and a small amount of an anti-hardening agent is coated on the surface of lithium hydroxide monohydrate. The dust free lithium hydroxide monohydrate is prepared by the following method: (1) preparing a 70±5 g/L LiOH solution with a concentration of Li2O being 70±5 g/L, wherein the concentration of SO4 2- is controlled to be lower than or equal to 15 g/L; (2) evaporating the LiOH solution obtained in Step (1) to a liquid-to-solid-ratio of 1:0.8-1.5, then adding a small amount of the anti-hardening agent, stirring uniformly, separating, and washing to obtain the wet dust-free LiOHH2O, which does not harden in vacuum sealed package in 3-5 months.
Description
= Dust-free Grade Lithium Hydroxide Monohydrate and Its Preparation Method Technical Field The present invention relates to a dust-free grade lithium hydroxide monohydrate and its preparation method thereof, belonging to the technical field of lithium hydroxide preparation.
Technical Background Lithium hydroxide monohydrate (Li0H.1-120) is widely applied, of which manufacturing of advanced lithium base grease is its greatest consumption field. Lithium base grease produced with Li0H. H20 is featured in wide applicable temperature range (-50 C to +300 C), good fireproof performance, resistant to oxidation, stable performance in case of repeated heating-cooling-heating cycle, long service life and strong water resistance. In addition, Li01-1. H20 is also widely used in the fields of chemical, national defense and battery, etc. As alkaline storage battery additive in the battery industry, it can extend the service life and increase the storage capacity of battery, while being ion exchange resin in defense field, it can absorb radioisotopes, thus being used as a reactor heat carrier and a metal surface protecting agent. In terms of aerospace, Li0H-H20 can be used for air purification in submarine and the pilot's breathing mask. In addition, Li01-1- H20 can also be used as water purifying agent, emulsifier for production of porous concretes as well as raw material of special optical glass, synthetic vitamin A and a lot of other lithium salts.
Preparation methods of Li011.H20 mainly include:
1. Limestone calcinations process Firstly, Lithium-containing ore and limestone are mixed and milled as per the specific mass ratio, then, the milled slurry is placed into a rotary kiln for calcination, during which CaO generated from decomposition of calcium carbonate is reacted with lithium ore to generate Li0H. However, this process has rarely been applied due to high energy consumption, large material liquidity, high cost, difficult to improve product quality.
Technical Background Lithium hydroxide monohydrate (Li0H.1-120) is widely applied, of which manufacturing of advanced lithium base grease is its greatest consumption field. Lithium base grease produced with Li0H. H20 is featured in wide applicable temperature range (-50 C to +300 C), good fireproof performance, resistant to oxidation, stable performance in case of repeated heating-cooling-heating cycle, long service life and strong water resistance. In addition, Li01-1. H20 is also widely used in the fields of chemical, national defense and battery, etc. As alkaline storage battery additive in the battery industry, it can extend the service life and increase the storage capacity of battery, while being ion exchange resin in defense field, it can absorb radioisotopes, thus being used as a reactor heat carrier and a metal surface protecting agent. In terms of aerospace, Li0H-H20 can be used for air purification in submarine and the pilot's breathing mask. In addition, Li01-1- H20 can also be used as water purifying agent, emulsifier for production of porous concretes as well as raw material of special optical glass, synthetic vitamin A and a lot of other lithium salts.
Preparation methods of Li011.H20 mainly include:
1. Limestone calcinations process Firstly, Lithium-containing ore and limestone are mixed and milled as per the specific mass ratio, then, the milled slurry is placed into a rotary kiln for calcination, during which CaO generated from decomposition of calcium carbonate is reacted with lithium ore to generate Li0H. However, this process has rarely been applied due to high energy consumption, large material liquidity, high cost, difficult to improve product quality.
2. Beta-spodumene sodium carbonate pressure extraction method First, Alpha-spodumene concentrate is transformed into beta-spodumene after being calcined at temperature of 1050 C to 1100 C in the rotary kiln, then, add and evenly mix a certain amount of Na2CO3, which is leached after being heated to 200 C, the soluble LiHCO3 is then generated by introducing CO2, the residue is then removed by filtration, add the purified lime milk as per the stoichiometric proportion, thus, Li011. H20 is prepared as the reaction liquid is concentrated and crystallized.
3. Lithium carbonate causticizing method Mix the purified lime milk with lithium carbonate in certain proportion, adjust the mixture to a certain caustic solution concentration, and then heat it to boiling while stirring vigorously. The causticizing reaction is as follows:
Ca(OH)2 + Li2CO3 = CaC031+ 2LiOH
3.5% LiOH solution can be obtained by the reaction. Insoluble residue (mainly CaCO3) is removed and mother liquor is separated, concentrated and crystallized to obtain lithium hydroxide monohydrate. Lithium hydroxide monohydrate is dried at 130 C to 140 C and then heated at 150 C to 180 C under reduced pressure to prepare anhydrous LiOH. Lithium carbonate causticizing method is the main method for producing lithium hydroxide both at home and especially abroad. However, this production process featured in complex process, large investment in equipment and high cost. Besides, the main raw material is lithium carbonate, the price of which directly affects the production cost of lithium hydroxide monohydrate.
Ca(OH)2 + Li2CO3 = CaC031+ 2LiOH
3.5% LiOH solution can be obtained by the reaction. Insoluble residue (mainly CaCO3) is removed and mother liquor is separated, concentrated and crystallized to obtain lithium hydroxide monohydrate. Lithium hydroxide monohydrate is dried at 130 C to 140 C and then heated at 150 C to 180 C under reduced pressure to prepare anhydrous LiOH. Lithium carbonate causticizing method is the main method for producing lithium hydroxide both at home and especially abroad. However, this production process featured in complex process, large investment in equipment and high cost. Besides, the main raw material is lithium carbonate, the price of which directly affects the production cost of lithium hydroxide monohydrate.
4. Electrolysis of refined brine Concentrate the brine until it contains 5% to 7% of Li (LiC1 is measured at rate of 35% to 44%) , then adjust pH into 10.5 to 11.5 after being filtered,, remove calcium and magnesium ions in brine to obtain purified brine (with LiC1 as the main ingredient) by precipitation; the purified brine is electrolysed as electrolytic solution in special electrolytic tank, wherein the anolyte is of purified brine and the catholyte is of water or LiOH solution; There is a cation permselective membrane between the anolyte and catholyte (such as perfluorosulfonic acid membrane Rf-S03H and perfluorocarboxylic acid membrane Rf-COOH, etc.), where cation can pass though but anion is blocked. During electrolysis, Li+ can migrate through the membrane to the cathode and be converted to LiOH. H2 and C12 produced by the reaction can be used as byproducts for producing HC1. Finally, LiOH solution at concentration of about 14% can be obtained in the cathode, thus, LiOH product can be produced after being crystallized and dried. However, this method is disadvantaged in great energy consumption, high cost and serious impact on the environment.
5. Electrolysis of Li2SO4 solution Li2SO4 solution as anolyte and water as catholyte is electrolyzed in membrane electrolytic tank, wherein anolyte and catholyte is separated by fluorine-containing cation exchange resin (such as C2H4 and CF2=CFO(CF2)3COCF3 copolymer), the control voltage is controlled to be 6V and the current density is controlled to be 100A/dm2 so as to obtain LiOH solution with mass concentration of about 10% in the cathode and H2SO4 solution in the anode. Ion-exchange membrane electrolysis method for preparation of LiOH is featured in high Li recovery rate (nearly 100%), no secondary pollution and high purity (> 99%) of the obtained product which can be directly used in the production of lithium lubricant. However, the present method requires higher impurity ion content of the purified brine, namely the total concentration of Na + and K+ should be below 5%, and the total amount of Ca2+ and Mg2+ should not be more than 0.004 4. In addition, the ion-exchange membrane is expensive and difficult for maintenance, resulting in higher production cost of LiOH.
6. Lithium aluminate precipitation method The method for preparing lithium hydroxide is to use sodium aluminate at concentration of 10% as the raw material, Al(OH)3 is prepared by carbonization of CO2 with concentration of 40%, then add it into the boron-abstracted brine (containing 0.13% of Li) at aluminum-to-lithium weight ratio of 13 to 15 , during which pH is at 6.8 to 7.0 and temperature at 90 C
, wherein Al(OH)3 can react with Li+ in brine to produce stable lithium aluminum compound (LiC1.2A1(OH)3-nH20) precipitate, with lithium aluminum precipitate yield of 95%, then, calcine the obtained lithium aluminum precipitate in the presence of neutral salts (e.g., NaNO3, NaCl, etc.) at 120 C to 130 C for 20 to 30 minutes so as to decompose into Al(OH)3 and soluble lithium salt, lithium and aluminum in the precipitate can be separated by hot water leaching. Let the leached solution flow through exchange column filled with strongly acidic cation exchange resin, Lit, Mg2+
and other cations are substituted and left in the exchange column, elute it with 1% to 20% aqueous caustic so that Mg2+, Ca2+ and other impurity ions generate hydroxide precipitates and remain in the exchange column while Li+ generates LiOH to flow out with the solution; or making the leaching solution flow through exchange column filled with strongly basic anion exchange resin, LiC1 in the solution is converted into LiOH and flow out with the solution, while Mg2+, Ca2+ and other impurity ions are precipitated and remained in the exchange column to be separated. The LiOH
solution concentration obtained by the present method is about 6%, and the recovery rate of lithium is more than 90%. The obtained LiOH solution is concentrated by evaporation, crystallized and dried to obtain LiOH product. The recovered calcined soda and aluminum hydroxide from the carbonation mixture is calcined at 900 C and then leached, wherein the leached sodium aluminate can be recycled. The disadvantage of this method for the scaled production lies in that the obtained lithium aluminum precipitate is colloid, the solid weight accounts for only about 10%
and the average particle is only 1 pm, so, it is difficult to be filtered, resulting in complex process and high energy consumption.
, wherein Al(OH)3 can react with Li+ in brine to produce stable lithium aluminum compound (LiC1.2A1(OH)3-nH20) precipitate, with lithium aluminum precipitate yield of 95%, then, calcine the obtained lithium aluminum precipitate in the presence of neutral salts (e.g., NaNO3, NaCl, etc.) at 120 C to 130 C for 20 to 30 minutes so as to decompose into Al(OH)3 and soluble lithium salt, lithium and aluminum in the precipitate can be separated by hot water leaching. Let the leached solution flow through exchange column filled with strongly acidic cation exchange resin, Lit, Mg2+
and other cations are substituted and left in the exchange column, elute it with 1% to 20% aqueous caustic so that Mg2+, Ca2+ and other impurity ions generate hydroxide precipitates and remain in the exchange column while Li+ generates LiOH to flow out with the solution; or making the leaching solution flow through exchange column filled with strongly basic anion exchange resin, LiC1 in the solution is converted into LiOH and flow out with the solution, while Mg2+, Ca2+ and other impurity ions are precipitated and remained in the exchange column to be separated. The LiOH
solution concentration obtained by the present method is about 6%, and the recovery rate of lithium is more than 90%. The obtained LiOH solution is concentrated by evaporation, crystallized and dried to obtain LiOH product. The recovered calcined soda and aluminum hydroxide from the carbonation mixture is calcined at 900 C and then leached, wherein the leached sodium aluminate can be recycled. The disadvantage of this method for the scaled production lies in that the obtained lithium aluminum precipitate is colloid, the solid weight accounts for only about 10%
and the average particle is only 1 pm, so, it is difficult to be filtered, resulting in complex process and high energy consumption.
7. Calcination method Extract boron from brine and evaporate 50% of water, then calcine it at 700 C
for 2 hours so that magnesium chloride in brine becomes magnesium oxide by pyrolytic decomposition, with decomposition rate of 93%. Then it is leached by water, wherein the leaching solution (containing 0.14% of lithium) is added with lime milk and calcined soda to remove calcium and magnesium ions, and add Na3PO4 to precipitate Li3PO4, and Li3PO4precipitate is filtered and mixed with CaO
and A1203 at the ratio of 1:6:2, which is then calcined for 2 hours in resistance furnace at 2300 C, the calcined mixture is leached with hot water at 85 C to 95 C and filtered, the filtrate is concentrated by evaporation, crystallized and dried to obtain LiOH product.
The advantages of this method are as follows: lithium and magnesium and other resources can be comprehensively utilized, needing less chemical raw materials; calcination can remove impurities such as boron and magnesium to improve the purity of the lithium hydroxide. The disadvantages are as follows: the use of magnesium makes the process flow be complex, serious corrosion of equipment, great water evaporation and high energy consumption.
for 2 hours so that magnesium chloride in brine becomes magnesium oxide by pyrolytic decomposition, with decomposition rate of 93%. Then it is leached by water, wherein the leaching solution (containing 0.14% of lithium) is added with lime milk and calcined soda to remove calcium and magnesium ions, and add Na3PO4 to precipitate Li3PO4, and Li3PO4precipitate is filtered and mixed with CaO
and A1203 at the ratio of 1:6:2, which is then calcined for 2 hours in resistance furnace at 2300 C, the calcined mixture is leached with hot water at 85 C to 95 C and filtered, the filtrate is concentrated by evaporation, crystallized and dried to obtain LiOH product.
The advantages of this method are as follows: lithium and magnesium and other resources can be comprehensively utilized, needing less chemical raw materials; calcination can remove impurities such as boron and magnesium to improve the purity of the lithium hydroxide. The disadvantages are as follows: the use of magnesium makes the process flow be complex, serious corrosion of equipment, great water evaporation and high energy consumption.
8. The patent numbered ZL 200710051016.5 provides a method for preparation of battery-grade lithium hydroxide monohydrate.
This method includes the steps as follows: suitably concentrate lithium sulfate leaching solution by evaporation, add NaOH for reaction to remove Fe, Ca, Mn and other impurities by filtering, and then freeze it to -5 3 C, Na2SO4-10H20 can be filtered and separated, after then, concentrate the filtrate by evaporation and crystallize the concentrated filtrate to obtain crude Li0H. H20. Then further dissolve the crude Li011. H20 and add refinined agent to remove Na, wet solid Li0H. H20 is obtained after being cooled, crystallized and filtered, then dry it to obtain Li0H. H20 product.
This method includes the steps as follows: suitably concentrate lithium sulfate leaching solution by evaporation, add NaOH for reaction to remove Fe, Ca, Mn and other impurities by filtering, and then freeze it to -5 3 C, Na2SO4-10H20 can be filtered and separated, after then, concentrate the filtrate by evaporation and crystallize the concentrated filtrate to obtain crude Li0H. H20. Then further dissolve the crude Li011. H20 and add refinined agent to remove Na, wet solid Li0H. H20 is obtained after being cooled, crystallized and filtered, then dry it to obtain Li0H. H20 product.
9. Lithium silicate conversion method Lithium silicate conversion method is to melt the obtained lithium carbonate and silicic acid to generate lithium silicate, wherein lithium silicate is hydrolyzed to produce lithium hydroxide; while lithium sulfate conversion method is to convert lithium in brine into lithium sulfate, and then make lithium sulfate and barium hydroxide react to produce lithium hydroxide. At present, above two processes are not mature, and the study is still underway.
Li011-1120 obtained by above-mentioned method results in pungent dust. With the enhancement of people's awareness of environmental protection, friendly working environment is urgent, thus, the flying dust is imminent to be solved. Wet Li0H. H20 can solve the problem of flying dust but it results in caking. It will be caked if it is not used for two days and needs to be broken into small pieces before feeding. If it is not used for 3 to 4 days, it will become very hard block and difficult to use. If it is not used for over four days, it is difficult to beat even with a hammer and unable be used any more. Thus, it has high requirement for procurement and production, which has serious impact on its use. Therefore, it is a new issue for us to solve the caking problem of wet Li0H.H20 and flying dust of dry Li0H-1-120.
Summary of the Invention The present invention aims to solve the technical problem of caking for existing wet Li0H-1-120 and flying dust for dry Li011. H20 and provide a new Li0H-1-120, namely dust-free and non-caking lithium hydroxide monohydrate.
The technical solution of the present invention is as follows: lithium hydroxide monohydrate of the present invention is of a wet loose granular product, which can be stored for 3-5 months and still remain loose particles, without caking.
Said lithium hydroxide monohydrate is loose granular wet product, wherein its moisture content is <3.5%, a small amount of anti-caking agent is coated on the surface of the lithium hydroxide monohydrate, and the said anti-caking agent is one of sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, . sodium pyrophosphate, sodium lauryl sulfate, polyacrylamide, methyl pentanol, 3-ethylhexyl phosphoric acid or cellulose derivatives; one of sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide or sodium ferrocyanide is preferred; and the weight of the anti-caking agent 20- is 1 to 1 Oppm.
The dust-free lithium hydroxide monohydrate of the present invention is prepared in the following method:
(1) Preparing LiOH solution containing 70 5g/1 of Li20, wherein the concentration of S042- is controlled to be no more than 15g/1;
(2) Evaporating the LiOH solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, then adding anti-caking agent, stirring, separating and washing to obtain the dust-free industrial grade Li0H. H20 product which does not caked in vacuum sealed package within several months;
Wherein, as the anti-caking agent is added, the preferred temperature is 90-100 LII. When the temperature decreases to 90E below, the S042- content of the obtained wet product is significantly high.
Wherein, the anti-caking agent is one of sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, sodium pyrophosphate, sodium lauryl sulfate, polyacrylamide, methyl pentanol, 3-ethylhexyl phosphoric acid or cellulose derivatives. The weight ratio of anti-caking agent and LiOH
in material is 1:1000 to 1:10000.
Extra anti-caking agents will introduce new impurities resulting in excessive impurity content and substandard product. Too less anti-caking agent will result in unobvious effect of anti-caking.
Further more, in order to obtain battery grade Li0H.H20 with higher purity, in Step (1) the concentration of S042- is controlled to be no more than 8 g/l, and the concentration of Na20 is controlled to be no more than 2g/1, and the concentration of CaO is controlled to be no more than 0.01 g/1; and in Step (2), anti-caking agent is added after the LiOH solution is evaporated to 1: 0.8 ¨
1.1 of liquid-solid volume ratio.
Control of the liquid-solid ratio of the evaporation is to control the end of evaporation. Higher liquid-solid ratio and early ending of evaporation will affect productivity and crystallization, resulting in bad crystal form. However, lower liquid-solid ratio and delay of ending of evaporation will make the feed liquid concentration be too high and high content of impurity product.
Industrial grade product is allowed to contain more impurity than that of battery grade product, so, the feed liquid concentration can be higher than that of battery grade products at end of evaporation, namely, liquid-solid ratio for production of industrial grade product can be less than that of battery grade product at end of evaporation.
The anti-caking agent of the present invention can be: sodium or potassium salts, such as sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, sodium pyrophosphate or methyl pentanol, 3-ethylhexyl phosphoric acid, cellulose derivatives and so on.
The anti-caking agent of greater solubility is preferred, such as one of:
sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide and sodium ferrocyanide.
Insoluble anti-caking agents should not be used as possible as it could be, such as sodium aluminium silicate, tricalcium phosphate, amorphous silica and so on.
Due to its extremely low solubility, insoluble anti-caking agent has bad mixing effect in the slurry but the amount is a relatively large, which will result in too high impurity content in the product. Thus, insoluble anti-caking agent should be avoided. Meanwhile, lithium hydroxide monohydrate production environment is inorganic salt system. According to the principle of the dissolution in the similar chemical substances, it is better not use organic substance during selection of anti-caking agent.
Wherein, LiOH solution in Step (1) can be obtained by the existing technology or obtained by dissolving crude Li01-1. H20 in water to remove the impurities.
For example, 1)calcine lithium-containing ore and limestone and then remove the impurities to generate LiOH; 2)evenly mix beta-spodumene and Na2CO3, heat it at 200 C for leaching, introduce CO2 to generate soluble LiHCO3, add refined lime milk according to stoichiometric ratio for reaction, then remove the impurities to generate LiOH; 3)lime milk reacts with lithium carbonate to generate LiOH solution; electrolyze purified brine to generate LiOH solution;
electrolyze Li2SO4 solution to generate LiOH solution; 4)carbonate sodium aluminate with CO2 for decomposition to obtain Al(OH)3, then react with brine to produce a stable compound lithium aluminum (LiC1.2A1(OH)3.nH20) precipitate, calcine at the presence of neutral salts (such as NaNO3, NaCl, etc.) so that it will be decomposed into Al(OH)3 and soluble lithium salt, leaching in hot water, making it flow through the exchange column with strongly acidic cation exchange resin to remove impurities so that Li + will generate LiOH and flow out; and 5)add NaOH to lithium sulfate for reaction to remove Fe, Ca, Mn and other impurities by filtration, and then freeze it to -5 3 C, separate Na2SO4. 10H20 by filtration, then concentrate the filtrate by evaporation to crystallize crude Li01-1. 1120, redissolve Li0H-1120 to obtain LiOH solution and so on, wherein said LiOH
solution contains Li20 70 5g/1 with the concentration of S042- no more than 8g/L, the concentration of Na20 no more than 2g/1 and the concentration of CaO no more than 0.01g/l.
The key of the present invention lies in that a small amount of additives (said additives is anti-caking agent.) which, without affecting the product quality of Li011.
H20, is added to regulate LiOH crystallization and precipitation process to prevent the wet precipitated product Li0H. 1120 from caking in the stored process and avoid flying dust after drying.
In order not to introduce new impurities, deionized water should be used as much as possible in the process of preparation of the solution'and elution.
The present invention is advanced in simple production process, easy operation, less investment in equipment, lower product cost, high recovery of lithium, stable product quality and no pungent flying dust. The produced dust-free Li0H-1120 product can fully meet the quality demand of the downstream industry and environment-friendly.
Embodiments of invention Example 1: Preparation of battery grade dust-free Li011.1120 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38g/L, adding Ca(OH)2 to adjust pH to 7, filtering, adding 1080g of sodium hydroxide to the filtrate, and _ sufficiently stirring to make it completely dissolve, and then stirring and cooling it to -3V C. When the concentration of S042- in the solution is 35g/L,filtering and separating to obtain LiOH solution and Na2SO4.10H20 solid. Evaporating the LiOH solution to volume ratio of liquid-solid about 0.8:1, - filtering and separating to obtain crude Li011- H20; adding deionized water and stirring to make it completely dissolve and make Li20 concentration in the solution be 70 g/L.
Adding 7.8 g of refined agent Li1.3Ti0.8Ceo.4Zro.5Alo.3(PO4)3, keeping the temperature at 45 C , stirring for 120 minutes, and then filtering and separating to obtain the filtrate, which is pure LiOH
liquid; wherein said LiOH
solution contains Li20 of concentration of 72g/1, and the S042- concentration is controlled to be 8g/L, the Na20 concentration be 2g/1 and the CaO concentration be 0.01g/l.
(2) Preparation of dust-free LiOH =H20 by crystallization process Evaporating the LiOH solution obtained in Step (1) to liquid-solid volume ratio of 1:0.9, then adding anti-caking agent sodium dodecyl sulfate, stirring, maintaining material temperature to be no less than 90 C, centrifugating and washing to obtain the solid battery grade dust-free Li011.1120 which is not caked in vacuum sealed package within five months.
Example 2-24: Preparation of battery grade dust-free Li011.1120 The preparation process is the same as that of Embodiment 1, and the only difference is quantity and type of anti-caking agent. Specific results are shown in Table 1.
Table 1 , No local No local No local Anti-caking No local Qualification of caking caking caking Examples Type of dispersant agent thecaking products within 5 within 1 within 5 proportion within 3 days month months months Sodium dodecyl Qualified 1 1:1000 4 4 4 4 sulphonate .
Sodium dodecyl 2 1:10000 Qualified 4 4 4 4 sulphonate Sodium dodecyl 3 1:5000 Qualified 4 4 4 4 sulphonate 4 Sodium ferrocyanide 1:800 Qualified 4 -\I
- X X
Sodium ferrocyanide 1:500 Qualified 4 4 - 4 x 6 Sodium ferrocyanide 1:1000 Qualified 4 4 X X
Fatty acid 7 polyethylene glycol 1:1000 Qualified 4 x x x ester Fatty acid 8 polyethylene glycol 1:800 Qualified 4 x x x ester Potassium 9 1:5000 Qualified 4 4 4 4 ferrocyanide Potassium 1:1000 Qualified 4 4 4 4 ferro cyanide Potassium 11 1:10000 Qualified ferro cyanide Sodium 12 1:1000 Qualified 4 4 X X+
hexametahposphate Sodium 13 1:800 4 4 x X+
hexametahposphate Qualified Sodium _ 14 1:500 4 4 X X
hexametahposphate Qualified _ Sodium 1:1000 4 x X X+
pyrophosphate Qualified Sodium _ 16 1:800 4 x X X
pyrophosphate Qualified Sodium _ 17 1:500 4 x x x pyrophosphate Qualified Sodium 18 1:1000 4 X X
silicoaluminate Qualified .
Sodium Excessive 19 1:500 4 x x x+
silicoaluminate sodium .
Tricalcium phosphate 1:1000 x x+ x+ x+
Qualified _ Excessive+ + x+
21 Tricalcium phosphate 1:500 4 x x calcium -Trimeric sodium + +
22 1:800 4 x x x phosphate Qualified , Trimeric sodium 23 1:500 4 X X+ X+
phosphate Qualified _ , Trimeric sodium 24 11000 X X+ X+ X+
phosphate Qualified .Ni in Table 1 indicates no caking, x indicates caking and, x+ indicates hard caking.
= Qualified mentioned in Table 1 means conformity to the battery grade standard indicators:
Fe% Na% K% S042-% CO2% Ca% HC1 insolubles Water insolubles <0.0008 <0.005 <0.005 <0.002 <0.010 <0.50 <0.005 <0.005 <0.005 According to the results in Table 1, in terms of selection of anti-caking agent, attention should be paid to the impact of the introduced substances on the content of product impurities. Meanwhile, some anti-caking agent will produce much foam to seriously affect the production progress. Thus, the good anti-caking agent includes sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide and sodium ferrocyanide. Insoluble anti-caking agent compounds could easily lead to excessive content of impurities and can not be used.
Example 25-48: Preparation of industrial grade dust-free Li011.H20 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38g/L, adding Ca(OH)2 to adjust pH to 7, filtering, adding 1080g of sodium hydroxide to the filtrate, and sufficiently stirring to make it completely dissolve, and then stirring and cooling it to -3 V ,When the concentration of S042- in the solution is 3 5g/L, filtering and separating to obtain LiOH solution and Na2SO4. 10H20 solid. Evaporating the LiOH solution to volume ratio of liquid-solid about 0.8:1, filtering and separating to obtain crude Li011. H20; adding deionized water and stirring to make it completely dissolve and make Li20 concentration in the solution be 70 g/L.Filtering and separating to obtain the filtrate, which is pure LiOH liquid; wherein said LiOH solution contains Li20 of concentration of 70g/1, and the S042- of concentration is controlled to be 12g/L, and the Na20 concentration be 5g/1 and CaO concentration be 0.06g/l.
(2) Preparation of dust-free Li011.1120 by crystallization process Evaporating the LiOH solution obtained in Step (1) to liquid-solid volume ratio of 1:1.2, then adding anti-caking agent, stirring, maintaining material temperature to be no less than 90 C, centrifugating and washing to obtain the solid industrial grade dust-free Li0H. H20, its caking situation in vacuum sealed package can be seen in Table 2.
Table 2 _ No local No local No local No local Anti-caking Qualification caking caking caking caking Examples Type of dispersant of the agent products within 5 within 1 within 3 within 5 proportion days month months months Sodium dodecyl 25 1:1000 4 4 4 if sulphonate Qualified Sodium dodecyl 26 1:10000 if if if if sulphonate Qualified Sodium dodecyl 27 1:5000 if Ni if if sulphonate Qualified 28 Sodium ferrocyanide 1:800 if if x x Qualified 29 Sodium ferrocyanide 1:500 if if if X
Qualified 30 Sodium ferrocyanide 1:1000 if if X X
Qualified Fatty acid 31 polyethylene glycol 1:1000 if x x x Qualified ester Fatty acid 32 polyethylene glycol 1:800 if x x x Qualified ester Potassium 33 1:5000 if if if if ferrocyanide Qualified Potassium 34 1:1000 if if if if ferrocyanide Qualified Potassium 35 1:10000 if if if x+
ferrocyanide Qualified Sodium 36 1:1000 if if x x+
hexametahposphate Qualified Sodium 37 1:800 if if X
X+
hexametahposphate Qualified .
Sodium 38 1:500 if if x x+
hexametahposphate Qualified Sodium 39 1:1000 if X X
X+
pyrophosphate Qualified Sodium 40 1:800 if x X
X+
pyrophosphate Qualified Sodium 41 1:500 if x x x+
pyrophosphate Qualified Sodium 42 1:1000 Al x X
X+
silicoaluminate Qualified Sodium 43 1:500 if X X+
X+
silicoaluminate Qualified 44 Tricalcium phosphate 1:1000 if X
X+ X+
Qualified 45 Tricalcium phosphate 1:500 if X
X+ X+
Qualified Trimeric sodium 46 1:800 if X X+
X+
phosphate Qualified Trimeric sodium 47 1:500 if x x+
x+
phosphate Qualified Trimeric sodium 48 1:1000 if X X+
X+
phosphate Qualified
Li011-1120 obtained by above-mentioned method results in pungent dust. With the enhancement of people's awareness of environmental protection, friendly working environment is urgent, thus, the flying dust is imminent to be solved. Wet Li0H. H20 can solve the problem of flying dust but it results in caking. It will be caked if it is not used for two days and needs to be broken into small pieces before feeding. If it is not used for 3 to 4 days, it will become very hard block and difficult to use. If it is not used for over four days, it is difficult to beat even with a hammer and unable be used any more. Thus, it has high requirement for procurement and production, which has serious impact on its use. Therefore, it is a new issue for us to solve the caking problem of wet Li0H.H20 and flying dust of dry Li0H-1-120.
Summary of the Invention The present invention aims to solve the technical problem of caking for existing wet Li0H-1-120 and flying dust for dry Li011. H20 and provide a new Li0H-1-120, namely dust-free and non-caking lithium hydroxide monohydrate.
The technical solution of the present invention is as follows: lithium hydroxide monohydrate of the present invention is of a wet loose granular product, which can be stored for 3-5 months and still remain loose particles, without caking.
Said lithium hydroxide monohydrate is loose granular wet product, wherein its moisture content is <3.5%, a small amount of anti-caking agent is coated on the surface of the lithium hydroxide monohydrate, and the said anti-caking agent is one of sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, . sodium pyrophosphate, sodium lauryl sulfate, polyacrylamide, methyl pentanol, 3-ethylhexyl phosphoric acid or cellulose derivatives; one of sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide or sodium ferrocyanide is preferred; and the weight of the anti-caking agent 20- is 1 to 1 Oppm.
The dust-free lithium hydroxide monohydrate of the present invention is prepared in the following method:
(1) Preparing LiOH solution containing 70 5g/1 of Li20, wherein the concentration of S042- is controlled to be no more than 15g/1;
(2) Evaporating the LiOH solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, then adding anti-caking agent, stirring, separating and washing to obtain the dust-free industrial grade Li0H. H20 product which does not caked in vacuum sealed package within several months;
Wherein, as the anti-caking agent is added, the preferred temperature is 90-100 LII. When the temperature decreases to 90E below, the S042- content of the obtained wet product is significantly high.
Wherein, the anti-caking agent is one of sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, sodium pyrophosphate, sodium lauryl sulfate, polyacrylamide, methyl pentanol, 3-ethylhexyl phosphoric acid or cellulose derivatives. The weight ratio of anti-caking agent and LiOH
in material is 1:1000 to 1:10000.
Extra anti-caking agents will introduce new impurities resulting in excessive impurity content and substandard product. Too less anti-caking agent will result in unobvious effect of anti-caking.
Further more, in order to obtain battery grade Li0H.H20 with higher purity, in Step (1) the concentration of S042- is controlled to be no more than 8 g/l, and the concentration of Na20 is controlled to be no more than 2g/1, and the concentration of CaO is controlled to be no more than 0.01 g/1; and in Step (2), anti-caking agent is added after the LiOH solution is evaporated to 1: 0.8 ¨
1.1 of liquid-solid volume ratio.
Control of the liquid-solid ratio of the evaporation is to control the end of evaporation. Higher liquid-solid ratio and early ending of evaporation will affect productivity and crystallization, resulting in bad crystal form. However, lower liquid-solid ratio and delay of ending of evaporation will make the feed liquid concentration be too high and high content of impurity product.
Industrial grade product is allowed to contain more impurity than that of battery grade product, so, the feed liquid concentration can be higher than that of battery grade products at end of evaporation, namely, liquid-solid ratio for production of industrial grade product can be less than that of battery grade product at end of evaporation.
The anti-caking agent of the present invention can be: sodium or potassium salts, such as sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, sodium pyrophosphate or methyl pentanol, 3-ethylhexyl phosphoric acid, cellulose derivatives and so on.
The anti-caking agent of greater solubility is preferred, such as one of:
sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide and sodium ferrocyanide.
Insoluble anti-caking agents should not be used as possible as it could be, such as sodium aluminium silicate, tricalcium phosphate, amorphous silica and so on.
Due to its extremely low solubility, insoluble anti-caking agent has bad mixing effect in the slurry but the amount is a relatively large, which will result in too high impurity content in the product. Thus, insoluble anti-caking agent should be avoided. Meanwhile, lithium hydroxide monohydrate production environment is inorganic salt system. According to the principle of the dissolution in the similar chemical substances, it is better not use organic substance during selection of anti-caking agent.
Wherein, LiOH solution in Step (1) can be obtained by the existing technology or obtained by dissolving crude Li01-1. H20 in water to remove the impurities.
For example, 1)calcine lithium-containing ore and limestone and then remove the impurities to generate LiOH; 2)evenly mix beta-spodumene and Na2CO3, heat it at 200 C for leaching, introduce CO2 to generate soluble LiHCO3, add refined lime milk according to stoichiometric ratio for reaction, then remove the impurities to generate LiOH; 3)lime milk reacts with lithium carbonate to generate LiOH solution; electrolyze purified brine to generate LiOH solution;
electrolyze Li2SO4 solution to generate LiOH solution; 4)carbonate sodium aluminate with CO2 for decomposition to obtain Al(OH)3, then react with brine to produce a stable compound lithium aluminum (LiC1.2A1(OH)3.nH20) precipitate, calcine at the presence of neutral salts (such as NaNO3, NaCl, etc.) so that it will be decomposed into Al(OH)3 and soluble lithium salt, leaching in hot water, making it flow through the exchange column with strongly acidic cation exchange resin to remove impurities so that Li + will generate LiOH and flow out; and 5)add NaOH to lithium sulfate for reaction to remove Fe, Ca, Mn and other impurities by filtration, and then freeze it to -5 3 C, separate Na2SO4. 10H20 by filtration, then concentrate the filtrate by evaporation to crystallize crude Li01-1. 1120, redissolve Li0H-1120 to obtain LiOH solution and so on, wherein said LiOH
solution contains Li20 70 5g/1 with the concentration of S042- no more than 8g/L, the concentration of Na20 no more than 2g/1 and the concentration of CaO no more than 0.01g/l.
The key of the present invention lies in that a small amount of additives (said additives is anti-caking agent.) which, without affecting the product quality of Li011.
H20, is added to regulate LiOH crystallization and precipitation process to prevent the wet precipitated product Li0H. 1120 from caking in the stored process and avoid flying dust after drying.
In order not to introduce new impurities, deionized water should be used as much as possible in the process of preparation of the solution'and elution.
The present invention is advanced in simple production process, easy operation, less investment in equipment, lower product cost, high recovery of lithium, stable product quality and no pungent flying dust. The produced dust-free Li0H-1120 product can fully meet the quality demand of the downstream industry and environment-friendly.
Embodiments of invention Example 1: Preparation of battery grade dust-free Li011.1120 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38g/L, adding Ca(OH)2 to adjust pH to 7, filtering, adding 1080g of sodium hydroxide to the filtrate, and _ sufficiently stirring to make it completely dissolve, and then stirring and cooling it to -3V C. When the concentration of S042- in the solution is 35g/L,filtering and separating to obtain LiOH solution and Na2SO4.10H20 solid. Evaporating the LiOH solution to volume ratio of liquid-solid about 0.8:1, - filtering and separating to obtain crude Li011- H20; adding deionized water and stirring to make it completely dissolve and make Li20 concentration in the solution be 70 g/L.
Adding 7.8 g of refined agent Li1.3Ti0.8Ceo.4Zro.5Alo.3(PO4)3, keeping the temperature at 45 C , stirring for 120 minutes, and then filtering and separating to obtain the filtrate, which is pure LiOH
liquid; wherein said LiOH
solution contains Li20 of concentration of 72g/1, and the S042- concentration is controlled to be 8g/L, the Na20 concentration be 2g/1 and the CaO concentration be 0.01g/l.
(2) Preparation of dust-free LiOH =H20 by crystallization process Evaporating the LiOH solution obtained in Step (1) to liquid-solid volume ratio of 1:0.9, then adding anti-caking agent sodium dodecyl sulfate, stirring, maintaining material temperature to be no less than 90 C, centrifugating and washing to obtain the solid battery grade dust-free Li011.1120 which is not caked in vacuum sealed package within five months.
Example 2-24: Preparation of battery grade dust-free Li011.1120 The preparation process is the same as that of Embodiment 1, and the only difference is quantity and type of anti-caking agent. Specific results are shown in Table 1.
Table 1 , No local No local No local Anti-caking No local Qualification of caking caking caking Examples Type of dispersant agent thecaking products within 5 within 1 within 5 proportion within 3 days month months months Sodium dodecyl Qualified 1 1:1000 4 4 4 4 sulphonate .
Sodium dodecyl 2 1:10000 Qualified 4 4 4 4 sulphonate Sodium dodecyl 3 1:5000 Qualified 4 4 4 4 sulphonate 4 Sodium ferrocyanide 1:800 Qualified 4 -\I
- X X
Sodium ferrocyanide 1:500 Qualified 4 4 - 4 x 6 Sodium ferrocyanide 1:1000 Qualified 4 4 X X
Fatty acid 7 polyethylene glycol 1:1000 Qualified 4 x x x ester Fatty acid 8 polyethylene glycol 1:800 Qualified 4 x x x ester Potassium 9 1:5000 Qualified 4 4 4 4 ferrocyanide Potassium 1:1000 Qualified 4 4 4 4 ferro cyanide Potassium 11 1:10000 Qualified ferro cyanide Sodium 12 1:1000 Qualified 4 4 X X+
hexametahposphate Sodium 13 1:800 4 4 x X+
hexametahposphate Qualified Sodium _ 14 1:500 4 4 X X
hexametahposphate Qualified _ Sodium 1:1000 4 x X X+
pyrophosphate Qualified Sodium _ 16 1:800 4 x X X
pyrophosphate Qualified Sodium _ 17 1:500 4 x x x pyrophosphate Qualified Sodium 18 1:1000 4 X X
silicoaluminate Qualified .
Sodium Excessive 19 1:500 4 x x x+
silicoaluminate sodium .
Tricalcium phosphate 1:1000 x x+ x+ x+
Qualified _ Excessive+ + x+
21 Tricalcium phosphate 1:500 4 x x calcium -Trimeric sodium + +
22 1:800 4 x x x phosphate Qualified , Trimeric sodium 23 1:500 4 X X+ X+
phosphate Qualified _ , Trimeric sodium 24 11000 X X+ X+ X+
phosphate Qualified .Ni in Table 1 indicates no caking, x indicates caking and, x+ indicates hard caking.
= Qualified mentioned in Table 1 means conformity to the battery grade standard indicators:
Fe% Na% K% S042-% CO2% Ca% HC1 insolubles Water insolubles <0.0008 <0.005 <0.005 <0.002 <0.010 <0.50 <0.005 <0.005 <0.005 According to the results in Table 1, in terms of selection of anti-caking agent, attention should be paid to the impact of the introduced substances on the content of product impurities. Meanwhile, some anti-caking agent will produce much foam to seriously affect the production progress. Thus, the good anti-caking agent includes sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide and sodium ferrocyanide. Insoluble anti-caking agent compounds could easily lead to excessive content of impurities and can not be used.
Example 25-48: Preparation of industrial grade dust-free Li011.H20 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38g/L, adding Ca(OH)2 to adjust pH to 7, filtering, adding 1080g of sodium hydroxide to the filtrate, and sufficiently stirring to make it completely dissolve, and then stirring and cooling it to -3 V ,When the concentration of S042- in the solution is 3 5g/L, filtering and separating to obtain LiOH solution and Na2SO4. 10H20 solid. Evaporating the LiOH solution to volume ratio of liquid-solid about 0.8:1, filtering and separating to obtain crude Li011. H20; adding deionized water and stirring to make it completely dissolve and make Li20 concentration in the solution be 70 g/L.Filtering and separating to obtain the filtrate, which is pure LiOH liquid; wherein said LiOH solution contains Li20 of concentration of 70g/1, and the S042- of concentration is controlled to be 12g/L, and the Na20 concentration be 5g/1 and CaO concentration be 0.06g/l.
(2) Preparation of dust-free Li011.1120 by crystallization process Evaporating the LiOH solution obtained in Step (1) to liquid-solid volume ratio of 1:1.2, then adding anti-caking agent, stirring, maintaining material temperature to be no less than 90 C, centrifugating and washing to obtain the solid industrial grade dust-free Li0H. H20, its caking situation in vacuum sealed package can be seen in Table 2.
Table 2 _ No local No local No local No local Anti-caking Qualification caking caking caking caking Examples Type of dispersant of the agent products within 5 within 1 within 3 within 5 proportion days month months months Sodium dodecyl 25 1:1000 4 4 4 if sulphonate Qualified Sodium dodecyl 26 1:10000 if if if if sulphonate Qualified Sodium dodecyl 27 1:5000 if Ni if if sulphonate Qualified 28 Sodium ferrocyanide 1:800 if if x x Qualified 29 Sodium ferrocyanide 1:500 if if if X
Qualified 30 Sodium ferrocyanide 1:1000 if if X X
Qualified Fatty acid 31 polyethylene glycol 1:1000 if x x x Qualified ester Fatty acid 32 polyethylene glycol 1:800 if x x x Qualified ester Potassium 33 1:5000 if if if if ferrocyanide Qualified Potassium 34 1:1000 if if if if ferrocyanide Qualified Potassium 35 1:10000 if if if x+
ferrocyanide Qualified Sodium 36 1:1000 if if x x+
hexametahposphate Qualified Sodium 37 1:800 if if X
X+
hexametahposphate Qualified .
Sodium 38 1:500 if if x x+
hexametahposphate Qualified Sodium 39 1:1000 if X X
X+
pyrophosphate Qualified Sodium 40 1:800 if x X
X+
pyrophosphate Qualified Sodium 41 1:500 if x x x+
pyrophosphate Qualified Sodium 42 1:1000 Al x X
X+
silicoaluminate Qualified Sodium 43 1:500 if X X+
X+
silicoaluminate Qualified 44 Tricalcium phosphate 1:1000 if X
X+ X+
Qualified 45 Tricalcium phosphate 1:500 if X
X+ X+
Qualified Trimeric sodium 46 1:800 if X X+
X+
phosphate Qualified Trimeric sodium 47 1:500 if x x+
x+
phosphate Qualified Trimeric sodium 48 1:1000 if X X+
X+
phosphate Qualified
Claims (8)
1. Lithium hydroxide monohydrate, characterized in that said lithium hydroxide monohydrate is loose granular wet product, containing no more than 3.5% of moisture, the surface of the lithium hydroxide monohydrate is wrapped with a small amount of anti-caking agent, said anti-caking agent is one of sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, sodium pyrophosphate, sodium lauryl sulfate, polyacrylamide, methyl pentanol, 3-ethylhexyl phosphoric acid or cellulose derivatives; and the weight of the anti-caking agent is 1 to 10ppm.
2. The lithium hydroxide monohydrate according to Claim 1, characterized in that said anti-caking agent is one of sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide or sodium ferrocyanide.
3. The lithium hydroxide monohydrate according to Claim 1 or 2, characterized in that it is prepared in the following method:
(1) Preparing LiOH solution containing 70~5g/l of Li2O, wherein the concentration of SO4 2- is controlled to be no more than 15g/l;
(2) Evaporating the LiOH solution obtained in Step (1) to liquid-solid volume ratio of 1:0.8 to 1.5, then adding anti-caking agent, stirring, separating and washing to obtain the dust-free and non-caking industrial grade LiOH.cndot.H2O product;
Wherein, when said anti-caking agent is added, the temperature of the LiOH
solution is maintained at 90°C to 100°C . The weight ratio of anti-caking agent and LiOH in material is 1:1000 to 1:10000.
(1) Preparing LiOH solution containing 70~5g/l of Li2O, wherein the concentration of SO4 2- is controlled to be no more than 15g/l;
(2) Evaporating the LiOH solution obtained in Step (1) to liquid-solid volume ratio of 1:0.8 to 1.5, then adding anti-caking agent, stirring, separating and washing to obtain the dust-free and non-caking industrial grade LiOH.cndot.H2O product;
Wherein, when said anti-caking agent is added, the temperature of the LiOH
solution is maintained at 90°C to 100°C . The weight ratio of anti-caking agent and LiOH in material is 1:1000 to 1:10000.
4. The lithium hydroxide monohydrate according to Claim 3, characterized in that in Step (1) , the concentration of SO4 2- is controlled to be no more than 8 g/l, the concentration of Na2O to be no more than 2g/l and the concentration of CaO to be no more than 0.01g/l.
5. The lithium hydroxide monohydrate according to Claim 3, characterized in that in Step (2), anti-caking agent is added after LiOH solution is evaporated to liquid-solid volume ratio of 1:0.8 to 1.1.
6. The method for preparing lithium hydroxide monohydrate, characterized in that it comprises the following steps:
(1) Preparing LiOH solution containing 70~5g/l of Li2O, wherein the concentration of SO4 2- is controlled to be no more than 15g/l;
(2) Evaporating LiOH obtained in Step (1) to liquid-solid volume ratio of 1:0.8 to 1.5, adding anti-caking agent, stirring, separating and washing to gain dust-free industrial grade LiOH.cndot.H2O product and then performing vacuum sealed packaging;
Wherein, when said anti-caking agent is added, the temperature of LiOH
solution is maintained at 90°C to 100°C , the anti-caking agent is one of sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, sodium pyrophosphate, sodium lauryl sulfate, polyacrylamide, methyl pentanol, 3-ethylhexyl phosphoric acid or cellulose derivatives. The weight ratio of anti-caking agent and LiOH in material is 1:1000 to 1:10000.
(1) Preparing LiOH solution containing 70~5g/l of Li2O, wherein the concentration of SO4 2- is controlled to be no more than 15g/l;
(2) Evaporating LiOH obtained in Step (1) to liquid-solid volume ratio of 1:0.8 to 1.5, adding anti-caking agent, stirring, separating and washing to gain dust-free industrial grade LiOH.cndot.H2O product and then performing vacuum sealed packaging;
Wherein, when said anti-caking agent is added, the temperature of LiOH
solution is maintained at 90°C to 100°C , the anti-caking agent is one of sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, trimeric sodium phosphate, sodium pyrophosphate, sodium lauryl sulfate, polyacrylamide, methyl pentanol, 3-ethylhexyl phosphoric acid or cellulose derivatives. The weight ratio of anti-caking agent and LiOH in material is 1:1000 to 1:10000.
7. The method for preparing lithium hydroxide monohydrate according to Claim 6, characterized in that in Step (1), the concentration of SO4 2- is controlled to be no more than 8 g/l, the concentration of Na2O to be no more than 2g/l and the concentration of CaO
to be no more than 0.01g/l.
to be no more than 0.01g/l.
8. The method for preparing lithium hydroxide monohydrate according to Claim 6, characterized in that in Step (2), anti-caking agent is added after the LiOH
solution is evaporated to liquid-solid volume ratio of 1:0.8 to 1.1.
solution is evaporated to liquid-solid volume ratio of 1:0.8 to 1.1.
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| WO2019220004A1 (en) * | 2018-05-18 | 2019-11-21 | Outotec (Finland) Oy | Method for recovering lithium hydroxide |
| CN112279279A (en) * | 2020-10-26 | 2021-01-29 | 荆门市格林美新材料有限公司 | Preparation method of battery-grade lithium hydroxide monohydrate |
| CN117548473A (en) * | 2023-12-20 | 2024-02-13 | 中国矿业大学(北京) | Stepped recycling and quality-classifying utilization method of coal gas slag |
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| CN102020294B (en) * | 2010-12-23 | 2012-04-25 | 雅安华汇锂业科技材料有限公司 | Lithium hydroxide monohydrate and preparation method thereof |
| RU2512310C2 (en) * | 2012-08-06 | 2014-04-10 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом"-Госкорпорация "Росатом" | Method of obtaining lithium ferrocyanide solution |
| CN102786069B (en) * | 2012-09-07 | 2014-02-12 | 雅安华汇锂业科技材料有限公司 | Preparation method of dust-free-level lithium hydroxide monohydrate |
| CN102838140B (en) * | 2012-09-14 | 2014-03-12 | 四川国润新材料有限公司 | Method for directly producing environment-friendly lithium hydroxide monohydrate from spodumene |
| CN104163442B (en) * | 2014-08-06 | 2016-03-23 | 四川天齐锂业股份有限公司 | Dustless stage monohydrate lithium hydroxide and preparation method |
| KR101839460B1 (en) | 2017-10-24 | 2018-03-16 | 성일하이텍㈜ | High-purity lithium carbonate recovery method from solution Containing Lithium |
| CN111889300A (en) * | 2020-06-16 | 2020-11-06 | 四川兴晟锂业有限责任公司 | Deposition and blocking prevention lithium hydroxide monohydrate crystal and preparation method thereof |
| CN112216834B (en) * | 2020-10-29 | 2021-08-03 | 湖南永杉锂业有限公司 | Method for preparing modified anhydrous lithium hydroxide by spray coating |
| CN113896214B (en) * | 2021-11-29 | 2023-03-21 | 福州大学 | Method for preparing high-purity lithium carbonate by adsorbing and carbonizing lithium sulfate solution |
| CN114276214B (en) * | 2021-12-10 | 2024-06-25 | 湖北宜化化工科技研发有限公司 | Production method for producing pentaerythritol by recycling carbide slag |
| CN115432721A (en) * | 2022-07-08 | 2022-12-06 | 江苏容汇通用锂业股份有限公司 | Process for preparing lithium hydroxide |
| CN115215357B (en) * | 2022-07-22 | 2023-11-24 | 江苏容汇通用锂业股份有限公司 | Method for preparing battery grade lithium hydroxide monohydrate from crude lithium sulfate |
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| WO2019220004A1 (en) * | 2018-05-18 | 2019-11-21 | Outotec (Finland) Oy | Method for recovering lithium hydroxide |
| EA039185B1 (en) * | 2018-05-18 | 2021-12-15 | Метсо Ототек Финланд Ой | Method for recovering lithium hydroxide |
| US11292725B2 (en) | 2018-05-18 | 2022-04-05 | Metso Outotec Finland Oy | Method for recovering lithium hydroxide |
| CN112279279A (en) * | 2020-10-26 | 2021-01-29 | 荆门市格林美新材料有限公司 | Preparation method of battery-grade lithium hydroxide monohydrate |
| CN112279279B (en) * | 2020-10-26 | 2023-05-12 | 荆门市格林美新材料有限公司 | Preparation method of battery grade lithium hydroxide monohydrate |
| CN117548473A (en) * | 2023-12-20 | 2024-02-13 | 中国矿业大学(北京) | Stepped recycling and quality-classifying utilization method of coal gas slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102020294A (en) | 2011-04-20 |
| WO2012083677A1 (en) | 2012-06-28 |
| CA2822196C (en) | 2016-10-18 |
| CN102020294B (en) | 2012-04-25 |
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