CA2822196C - 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
The present invention relates to a dust-free grade lithium hydroxide monohydrate and its preparation method thereof which belongs to the technical field of lithium hydroxide preparation.
The present invention is to provide a dust-free and non-caking lithium hydroxide monohydrate to solve the technical problem of caking for existing wet LiOH.cndot.H2O and flying dust for dry LiOH.cndot.H2O. The lithium hydroxide monohydrate of the present invention is a wet loose granular product, wherein the moisture content is no more than 3.5%, and a small amount of anti-caking agent is coated on the surface of the lithium hydroxide monohydrate. The dust-free lithium hydroxide monohydrate is prepared by 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; and (2) evaporating the LiOH solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1.5, then adding a small amount of anti-caking agent, stifling, separating and washing to obtain the wet dust-free LiOH.cndot.H2O product which is not caked in vacuum sealed package within 3 to 5 months.
The present invention is to provide a dust-free and non-caking lithium hydroxide monohydrate to solve the technical problem of caking for existing wet LiOH.cndot.H2O and flying dust for dry LiOH.cndot.H2O. The lithium hydroxide monohydrate of the present invention is a wet loose granular product, wherein the moisture content is no more than 3.5%, and a small amount of anti-caking agent is coated on the surface of the lithium hydroxide monohydrate. The dust-free lithium hydroxide monohydrate is prepared by 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; and (2) evaporating the LiOH solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1.5, then adding a small amount of anti-caking agent, stifling, separating and washing to obtain the wet dust-free LiOH.cndot.H2O product which is not caked in vacuum sealed package within 3 to 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+120) is widely applied, of which manufacturing of advanced lithium base grease is its greatest consumption field. Lithium base grease produced with Li0H+120 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, Li0114-120 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 1 5 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, Li0H+120 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 Li011.1120 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+120) is widely applied, of which manufacturing of advanced lithium base grease is its greatest consumption field. Lithium base grease produced with Li0H+120 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, Li0114-120 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 1 5 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, Li0H+120 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 Li011.1120 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, Li011-1-120 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 Li0H.
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 Li0H.
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 by products 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.
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 by products 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%. In addition, the ion-exchange membrane is expensive and difficult for maintenance, resulting in higher production cost of 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%. 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, A1(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 A1(OH)3 can react with Lì+ 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, NaCI, etc.) at 120 C to 130 C for 20 to 30 minutes so as to decompose into A1(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, Li, 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 11.1m, so, it is difficult to be filtered, resulting in complex process and high energy consumption.
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 11.1m, 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 Li3PO4 precipitate 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 Li3PO4 precipitate 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+120. Then further dissolve the crude Li0H+120 and add refinined agent to remove Na, wet solid Li0H+120 is obtained after being cooled, crystallized and filtered, then dry it to obtain Li0H-1120 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+120. Then further dissolve the crude Li0H+120 and add refinined agent to remove Na, wet solid Li0H+120 is obtained after being cooled, crystallized and filtered, then dry it to obtain Li0H-1120 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.
Li0H+120 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+120 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 1.,i0H= H20 and flying dust of dry' Li01-1-1-170.
Summary of the Invention The present invention relates to Li01-1=1-120 lithium hydroxide monohydrate, which is dust-free and non-caking.
The present invention relates to lithium hydroxide monohydrate which is a wet loose granular product, which may be stored for 3-5 months and still remain loose particles, 1 0 without caking.
Said lithium hydroxide monohydrate may be a 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 is 1 to 10 ppm.
One aspect of the invention relates to lithium hydroxide monohydrate, characterized in that said lithium hydroxide monohydrate (1.,i01-11-1)0) is a loose granular wet product, containing Li0I-1=1-120 and from 1.5 to 3.5% by weight of moisture, wherein the surface of the LiOITH70 granules is coated with an anti-caking agent, 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, and 3-ethylhexyl phosphoric acid; and wherein the weight ratio of the anti-caking agent to 1_,i0H is from 1 to 10 ppm.
The dust-free lithium hydroxide monohydrate of the present invention may be prepared in the following method:
(1) preparing LiOH solution containing 70+5 g/1 of Li70, wherein the concentration of S042- is controlled to be no more than 15 g/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 LiOH1120 product which does not caked in VaCULIM
sealed package within several months;
wherein, as the anti-caking agent is added, the preferred temperature is 90-100 C. When the temperature decreases to 90 C below, the S042- content of the obtained wet product may be 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 may be 1:500 to 1:10000.
A further aspect relates to a method for preparing lithium hydroxide monohydrate, which comprises the following steps: (1) preparing an aqueous Li011 solution, in which equivalent 1.,i20 concentration is 70+5 g/l, the solution being free of S042- or having a S042- concentration of no more than 15 g/1; (2) evaporating the LiOH
solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, adding the anti-caking agent, stirring, and separating and washing an obtained solid to obtain a loose granular wet product and then performing vacuum sealed packaging; wherein said anti-caking agent is added in a weight ratio of between 1:1000 and 1:10000 relative to LiOH, wherein, when said anti-caking agent is added, the temperature of the LiOH solution is maintained at 90 C to 100 C, 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, and 3-ethylhexyl phosphoric acid.
Extra anti-caking agents may introduce new impurities resulting in excessive impurity content and substandard product. Too little anti-caking agent may result in unobvious =
effect of anti-caking.
Further more, in order to obtain battery grade LiOH=E120 with higher purity, in Step (1) the concentration of S042- may be controlled to be no more than 8 g/1, and the concentration of Na2O may be controlled to be no more than 2 g/1, and the concentration of CaO may be controlled to be no more than 0.01 g/1; and in Step (2), anti-caking agent may be 1 0 added after the 1.i014 solution is evaporated to 1:0.8 ¨ 1.1 of liquid-solid volume ratio.
Control of the liquid-solid ratio of the evaporation may be to control the end of evaporation. Higher liquid-solid ratio and early ending of evaporation may affect productivity and crystallization, resulting in had crystal form. However, lower liquid-solid ratio and delay of ending of evaporation may make the feed liquid concentration be too high and high content 1 5 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.
7a 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 may 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 LiOH=1420 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 A1(OH)3, then react with brine to produce a stable compound lithium aluminum (LiC1.2A1(OH)311H20) precipitate, calcine at the presence of neutral salts (such as NaNO3, NaC1, etc.) so that it will be decomposed into A1(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 Li0H+120, redissolve LiOH=1420 to obtain LiOH solution and so on, wherein said LiOH solution contains Li20 70 5 g/1 with the concentration of S042- no more than 8 g/L, the concentration of Na2O no more than 2 g/1 and the concentration of CaO no more than 0.01 g/1.
Addition of a small amount of additives (said additives is anti-caking agent.) which, without affecting the product quality of LiOH=1420, may be added to regulate LiOH
crystallization and precipitation process to prevent the wet precipitated product Li01-1-1-120 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.
In some embodiments, the present invention may provide a 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+120 product may fully meet the quality demand of the downstream industry and environment-friendly.
According to one aspect of the present invention, there is provided lithium hydroxide monohydrate, characterized in that said lithium hydroxide monohydrate is a loose granular wet product, containing from 1.5 to 3.5% by weight of moisture, wherein the surface of the lithium hydroxide monohydrate is coated with an anti-caking agent, 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, and 3-ethylhexyl phosphoric acid; and wherein the weight of the anti-caking agent is 1 to lOppm.
According to another aspect of the present invention, there is provided a method for preparing lithium hydroxide monohydrate, which comprises the following steps:
(1) preparing an aqueous LiOH solution containing 70 5 g/1 of Li20, the solution being free of S042- or having a S042- concentration of no more than 15 g/I; (2) evaporating the LiOH
solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, adding the anti-caking agent, stirring, and separating and washing an obtained solid to obtain a loose granular wet product and then performing vacuum sealed packaging; wherein, when said anti-caking agent is added, the temperature of the LiOH solution is maintained at 90 C to 100 C, 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, and 3-ethylhexyl phosphoric acid;
and wherein the weight of the anti-caking agent is 1 to 10 ppm relative to the weight of the LiOH.
Embodiments of invention 1 5 Example 1: Preparation of battery grade dust-free Li011.1120 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5 g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38 g/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 C. When the concentration of S042- in the solution is 35 g/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 Li0H+120;
adding deionized water and stirring to make it completely dissolve and make Li20 concentration in the solution be 70 g/L. Adding 7.8g of refined agent Li' 3Tio 8Ce0 4Zr0 5A10 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 72 g/1, and the S042"
concentration is controlled to be 8 g/L, the Na20 concentration be 2 g/1 and the CaO
concentration be 0.01 g/1.
(2) Preparation of dust-free Li0H.1-120 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 Li01-1.1-120 which is not caked in vacuum sealed package within five months.
Example 2-24: Preparation of battery grade dust-free Li01-1.1-120 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 caking the products within 5 within 1 within 5 proportion within 3 days month months months Sodium dodecyl Qualified 1 1:1000 4 \I \I -4 sulphonate Sodium dodecyl 2 1:10000 Qualified 4 4 Ai 4 sulphonate Sodium dodecyl 3 1:5000 Qualified 4 4 4 4 sulphonate 4 Sodium ferrocyanide 1:800 Qualified 4 4 x x Sodium ferrocyanide 1:500 Qualified 4 4 4 x __ 6 Sodium ferrocyanide 1:1000 Qualified Ai Ai 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 \I 4 AI
ferrocyanide Potassium 11 1:10000 Qualified 4 4 4 x+
ferrocyanide Sodium 12 1:1000 Qualified 4 4 x xl hexametahposphate Sodium 13 1:800 4 4 x x+
hexametahposphate Qualified Sodium 14 1:500 4 4 x x+
hexametahposphate Qualified , Sodium pyrophosphate 1:1000 4 x x x' Qualified 16 Sodium pyrophosphate 1:800 4 x x x+
Qualified 17 Sodium pyrophosphate 1:500 4 x x x ' Qualified Sodium 18 1:1000 4 x x x+
silicoaluminate Qualified Sodium Excessive x' 19 1:500 4 x x silicoaluminate sodium Tricalcium phosphate 1:1000 x x ' x ' x' Qualified Excessive 21 Tricalcium phosphate 1:500 4 x+ x+ x+
calcium Trimeric sodium x+
22 1:800 4 x x+
phosphate Qualified Trimeric sodium 23 1:500 4 x x+ x+
phosphate Qualified Trimeric sodium x+
24 1:1000 x+ x+
phosphate Qualified l x 4 in Table I indicates no caking, x indicates caking and, x+ indicates hard caking.
=
Qualified mentioned in Table 1 means conformity to the battery grade standard indicators:
HC1 Water Fe% Na% K% C1-% S042-% CO2% Ca%
insolubles 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 L10111120 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5 g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38 g/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 C,When the concentration of 5042- in the solution is 35 g/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 Li0H+120;
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 70 g/1, and the S042- of concentration is controlled to be 12 g/L, and the Na20 concentration be 5 g/1 and CaO concentration be 0.06 g/1.
(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 LiOH=1420, 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 of caking caking caking caking Examples Type of dispersant agent the products within 5 within 1 within 3 within 5 proportion days month months months Sodium dodecyl 25 1:1000 A) \) A) A) sulphonate Qualified Sodium dodecyl 26 1:10000 sulphonate Qualified Sodium dodecyl 27 1:5000 Ai Ai Ai Ai sulphonate Qualified 28 Sodium ferrocyanide 1:800 Ai Ai x x Qualified 29 Sodium ferrocyanide 1:500 Al \i Ai X
Qualified 30 Sodium ferrocyanide 1:1000 Al Al X x Qualified Fatty acid polyethylene x AI
31 1:1000 x x glycol ester Qualified , Fatty acid polyethylene x 32 1:800 AI X X
glycol ester Qualified 33 Potassium ferrocyanide 1:5000 Ai Ai Ai Ai Qualified 34 Potassium ferrocyanide 1:1000 Ai AI Ai AI
Qualified 35 Potassium ferrocyanide 1:10000 Ai Ai Ai x+
Qualified Sodium 36 1:1000 AI \I x x*
hexametahposphate Qualified Sodium 37 1:800 V Ai x X +
hexametahposphate Qualified Sodium 38 1:500 Ai \/ x x ' hexametahposphate Qualified 39 Sodium pyrophosphate 1:1000 Ai X X X +
Qualified 40 Sodium pyrophosphate 1:800 Ai X X X ' Qualified 41 Sodium pyrophosphate 1:500 -AI X X X +
Qualified 42 Sodium silicoaluminate 1:1000 Al X X X +
Qualified 43 Sodium silicoaluminate 1:500 Ai x x+ x ' Qualified 44 Tricalcium phosphate 1:1000 Ai x x+ x' Qualified 45 Tricalcium phosphate 1:500 Ai x x' x ' Qualified Trimeric sodium 46 1:800 \I x x+ x+
phosphate Qualified Trimeric sodium 47 1:500 Ai X X + X +
phosphate Qualified Trimeric sodium 48 1:1000 Ai x x+ x+
phosphate Qualified
Li0H+120 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+120 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 1.,i0H= H20 and flying dust of dry' Li01-1-1-170.
Summary of the Invention The present invention relates to Li01-1=1-120 lithium hydroxide monohydrate, which is dust-free and non-caking.
The present invention relates to lithium hydroxide monohydrate which is a wet loose granular product, which may be stored for 3-5 months and still remain loose particles, 1 0 without caking.
Said lithium hydroxide monohydrate may be a 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 is 1 to 10 ppm.
One aspect of the invention relates to lithium hydroxide monohydrate, characterized in that said lithium hydroxide monohydrate (1.,i01-11-1)0) is a loose granular wet product, containing Li0I-1=1-120 and from 1.5 to 3.5% by weight of moisture, wherein the surface of the LiOITH70 granules is coated with an anti-caking agent, 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, and 3-ethylhexyl phosphoric acid; and wherein the weight ratio of the anti-caking agent to 1_,i0H is from 1 to 10 ppm.
The dust-free lithium hydroxide monohydrate of the present invention may be prepared in the following method:
(1) preparing LiOH solution containing 70+5 g/1 of Li70, wherein the concentration of S042- is controlled to be no more than 15 g/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 LiOH1120 product which does not caked in VaCULIM
sealed package within several months;
wherein, as the anti-caking agent is added, the preferred temperature is 90-100 C. When the temperature decreases to 90 C below, the S042- content of the obtained wet product may be 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 may be 1:500 to 1:10000.
A further aspect relates to a method for preparing lithium hydroxide monohydrate, which comprises the following steps: (1) preparing an aqueous Li011 solution, in which equivalent 1.,i20 concentration is 70+5 g/l, the solution being free of S042- or having a S042- concentration of no more than 15 g/1; (2) evaporating the LiOH
solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, adding the anti-caking agent, stirring, and separating and washing an obtained solid to obtain a loose granular wet product and then performing vacuum sealed packaging; wherein said anti-caking agent is added in a weight ratio of between 1:1000 and 1:10000 relative to LiOH, wherein, when said anti-caking agent is added, the temperature of the LiOH solution is maintained at 90 C to 100 C, 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, and 3-ethylhexyl phosphoric acid.
Extra anti-caking agents may introduce new impurities resulting in excessive impurity content and substandard product. Too little anti-caking agent may result in unobvious =
effect of anti-caking.
Further more, in order to obtain battery grade LiOH=E120 with higher purity, in Step (1) the concentration of S042- may be controlled to be no more than 8 g/1, and the concentration of Na2O may be controlled to be no more than 2 g/1, and the concentration of CaO may be controlled to be no more than 0.01 g/1; and in Step (2), anti-caking agent may be 1 0 added after the 1.i014 solution is evaporated to 1:0.8 ¨ 1.1 of liquid-solid volume ratio.
Control of the liquid-solid ratio of the evaporation may be to control the end of evaporation. Higher liquid-solid ratio and early ending of evaporation may affect productivity and crystallization, resulting in had crystal form. However, lower liquid-solid ratio and delay of ending of evaporation may make the feed liquid concentration be too high and high content 1 5 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.
7a 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 may 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 LiOH=1420 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 A1(OH)3, then react with brine to produce a stable compound lithium aluminum (LiC1.2A1(OH)311H20) precipitate, calcine at the presence of neutral salts (such as NaNO3, NaC1, etc.) so that it will be decomposed into A1(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 Li0H+120, redissolve LiOH=1420 to obtain LiOH solution and so on, wherein said LiOH solution contains Li20 70 5 g/1 with the concentration of S042- no more than 8 g/L, the concentration of Na2O no more than 2 g/1 and the concentration of CaO no more than 0.01 g/1.
Addition of a small amount of additives (said additives is anti-caking agent.) which, without affecting the product quality of LiOH=1420, may be added to regulate LiOH
crystallization and precipitation process to prevent the wet precipitated product Li01-1-1-120 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.
In some embodiments, the present invention may provide a 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+120 product may fully meet the quality demand of the downstream industry and environment-friendly.
According to one aspect of the present invention, there is provided lithium hydroxide monohydrate, characterized in that said lithium hydroxide monohydrate is a loose granular wet product, containing from 1.5 to 3.5% by weight of moisture, wherein the surface of the lithium hydroxide monohydrate is coated with an anti-caking agent, 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, and 3-ethylhexyl phosphoric acid; and wherein the weight of the anti-caking agent is 1 to lOppm.
According to another aspect of the present invention, there is provided a method for preparing lithium hydroxide monohydrate, which comprises the following steps:
(1) preparing an aqueous LiOH solution containing 70 5 g/1 of Li20, the solution being free of S042- or having a S042- concentration of no more than 15 g/I; (2) evaporating the LiOH
solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, adding the anti-caking agent, stirring, and separating and washing an obtained solid to obtain a loose granular wet product and then performing vacuum sealed packaging; wherein, when said anti-caking agent is added, the temperature of the LiOH solution is maintained at 90 C to 100 C, 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, and 3-ethylhexyl phosphoric acid;
and wherein the weight of the anti-caking agent is 1 to 10 ppm relative to the weight of the LiOH.
Embodiments of invention 1 5 Example 1: Preparation of battery grade dust-free Li011.1120 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5 g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38 g/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 C. When the concentration of S042- in the solution is 35 g/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 Li0H+120;
adding deionized water and stirring to make it completely dissolve and make Li20 concentration in the solution be 70 g/L. Adding 7.8g of refined agent Li' 3Tio 8Ce0 4Zr0 5A10 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 72 g/1, and the S042"
concentration is controlled to be 8 g/L, the Na20 concentration be 2 g/1 and the CaO
concentration be 0.01 g/1.
(2) Preparation of dust-free Li0H.1-120 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 Li01-1.1-120 which is not caked in vacuum sealed package within five months.
Example 2-24: Preparation of battery grade dust-free Li01-1.1-120 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 caking the products within 5 within 1 within 5 proportion within 3 days month months months Sodium dodecyl Qualified 1 1:1000 4 \I \I -4 sulphonate Sodium dodecyl 2 1:10000 Qualified 4 4 Ai 4 sulphonate Sodium dodecyl 3 1:5000 Qualified 4 4 4 4 sulphonate 4 Sodium ferrocyanide 1:800 Qualified 4 4 x x Sodium ferrocyanide 1:500 Qualified 4 4 4 x __ 6 Sodium ferrocyanide 1:1000 Qualified Ai Ai 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 \I 4 AI
ferrocyanide Potassium 11 1:10000 Qualified 4 4 4 x+
ferrocyanide Sodium 12 1:1000 Qualified 4 4 x xl hexametahposphate Sodium 13 1:800 4 4 x x+
hexametahposphate Qualified Sodium 14 1:500 4 4 x x+
hexametahposphate Qualified , Sodium pyrophosphate 1:1000 4 x x x' Qualified 16 Sodium pyrophosphate 1:800 4 x x x+
Qualified 17 Sodium pyrophosphate 1:500 4 x x x ' Qualified Sodium 18 1:1000 4 x x x+
silicoaluminate Qualified Sodium Excessive x' 19 1:500 4 x x silicoaluminate sodium Tricalcium phosphate 1:1000 x x ' x ' x' Qualified Excessive 21 Tricalcium phosphate 1:500 4 x+ x+ x+
calcium Trimeric sodium x+
22 1:800 4 x x+
phosphate Qualified Trimeric sodium 23 1:500 4 x x+ x+
phosphate Qualified Trimeric sodium x+
24 1:1000 x+ x+
phosphate Qualified l x 4 in Table I indicates no caking, x indicates caking and, x+ indicates hard caking.
=
Qualified mentioned in Table 1 means conformity to the battery grade standard indicators:
HC1 Water Fe% Na% K% C1-% S042-% CO2% Ca%
insolubles 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 L10111120 (1) Preparation of LiOH solution containing Li20 of concentration of 70 5 g/1 It includes the following steps:
Taking 10000m1 of Li2SO4 leaching solution containing Li20 of concentration of 38 g/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 C,When the concentration of 5042- in the solution is 35 g/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 Li0H+120;
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 70 g/1, and the S042- of concentration is controlled to be 12 g/L, and the Na20 concentration be 5 g/1 and CaO concentration be 0.06 g/1.
(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 LiOH=1420, 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 of caking caking caking caking Examples Type of dispersant agent the products within 5 within 1 within 3 within 5 proportion days month months months Sodium dodecyl 25 1:1000 A) \) A) A) sulphonate Qualified Sodium dodecyl 26 1:10000 sulphonate Qualified Sodium dodecyl 27 1:5000 Ai Ai Ai Ai sulphonate Qualified 28 Sodium ferrocyanide 1:800 Ai Ai x x Qualified 29 Sodium ferrocyanide 1:500 Al \i Ai X
Qualified 30 Sodium ferrocyanide 1:1000 Al Al X x Qualified Fatty acid polyethylene x AI
31 1:1000 x x glycol ester Qualified , Fatty acid polyethylene x 32 1:800 AI X X
glycol ester Qualified 33 Potassium ferrocyanide 1:5000 Ai Ai Ai Ai Qualified 34 Potassium ferrocyanide 1:1000 Ai AI Ai AI
Qualified 35 Potassium ferrocyanide 1:10000 Ai Ai Ai x+
Qualified Sodium 36 1:1000 AI \I x x*
hexametahposphate Qualified Sodium 37 1:800 V Ai x X +
hexametahposphate Qualified Sodium 38 1:500 Ai \/ x x ' hexametahposphate Qualified 39 Sodium pyrophosphate 1:1000 Ai X X X +
Qualified 40 Sodium pyrophosphate 1:800 Ai X X X ' Qualified 41 Sodium pyrophosphate 1:500 -AI X X X +
Qualified 42 Sodium silicoaluminate 1:1000 Al X X X +
Qualified 43 Sodium silicoaluminate 1:500 Ai x x+ x ' Qualified 44 Tricalcium phosphate 1:1000 Ai x x+ x' Qualified 45 Tricalcium phosphate 1:500 Ai x x' x ' Qualified Trimeric sodium 46 1:800 \I x x+ x+
phosphate Qualified Trimeric sodium 47 1:500 Ai X X + X +
phosphate Qualified Trimeric sodium 48 1:1000 Ai x x+ x+
phosphate Qualified
Claims (13)
1 . Lithium hydroxide monohydrate, characterized in that said lithium hydroxide monohydrate (LiOH H2O) is a loose granular wet product, containing LiOH H2O
and from
1.5 to 3.5% by weight of moisture, wherein the surface of the LiOH.cndot.H2O
granules is coated with an anti-caking agent, 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, and 3-ethylhexyl phosphoric acid; and wherein the weight ratio of the anti-caking agent to LiOH is from 1 to 10 ppm.
granules is coated with an anti-caking agent, 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, and 3-ethylhexyl phosphoric acid; and wherein the weight ratio of the anti-caking agent to LiOH is from 1 to 10 ppm.
2. The lithium hydroxide monohydrate according to claim 1, wherein the anti-caking agent is one of sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide and sodium ferrocyanide.
3. A method for preparing lithium hydroxide monohydrate, which comprises the following steps:
(1) preparing an aqueous LiOH solution, in which equivalent Li2O
concentration is 70 5 g/l, the solution being free of SO4 2- or having a SO4 2-concentration of no more than 15 g/l;
(2) evaporating the LiOH solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, adding the anti-caking agent, stirring, and separating and washing an obtained solid to obtain a loose granular wet product and then performing vacuum sealed packaging;
wherein said anti-caking agent is added in a weight ratio of between 1: 1 000 and 1:10000 relative to LiOH, wherein, when said anti-caking agent is added, the temperature of the LiOH
solution is maintained at 90°C to 100°C, 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, and 3-ethylhexyl phosphoric acid.
(1) preparing an aqueous LiOH solution, in which equivalent Li2O
concentration is 70 5 g/l, the solution being free of SO4 2- or having a SO4 2-concentration of no more than 15 g/l;
(2) evaporating the LiOH solution obtained in Step (1) to a liquid-solid volume ratio of 1:0.8 to 1:1.5, adding the anti-caking agent, stirring, and separating and washing an obtained solid to obtain a loose granular wet product and then performing vacuum sealed packaging;
wherein said anti-caking agent is added in a weight ratio of between 1: 1 000 and 1:10000 relative to LiOH, wherein, when said anti-caking agent is added, the temperature of the LiOH
solution is maintained at 90°C to 100°C, 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, and 3-ethylhexyl phosphoric acid.
4. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein in Step (1), the concentration of SO4 2- is no more than 8 g/l; wherein the solution is free of Na+ or has an equivalent Na2O concentration of no more than 2 g/l; and wherein the solution is free of Ca2+ or has an equivalent CaO concentration of no more than 0.01 g/l.
5. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein in Step (2), the anti-caking agent is added after the LiOH
solution is evaporated to a liquid-solid volume ratio of 1:0.8 to 1:1.1.
solution is evaporated to a liquid-solid volume ratio of 1:0.8 to 1:1.1.
6. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein the anti-caking agent is added in a weight ratio of between 1:1000 and 1:10000 relative to LiOH, and wherein the anti-caking agent is sodium dodecyl sulphonate.
7. The method for preparing lithium hydroxide monohydrate according to claim 3, which is prepared by a method wherein the anti-caking agent is added in a weight ratio of between 1:500 and 1:1000 relative to LiOH, and wherein the anti-caking agent is sodium ferrocyanide.
8. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein the anti-caking agent is added in a weight ratio of between 1:800 and 1:5000 relative to LiOH, and wherein the anti-caking agent is a fatty acid polyethylene glycol ester.
9. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein the anti-caking agent is added in a weight ratio of between 1:1000 and 1:10000 relative to LiOH, and wherein the anti-caking agent is potassium ferrocyanide.
10. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein the anti-caking agent is added in a weight ratio of between 1:500 and 1:1000 relative to LiOH, and wherein the anti-caking agent is sodium hexametaphosphate.
11. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein the anti-caking agent is added in a weight ratio of between 1:500 and 1:1000 relative to LiOH, and wherein the anti-caking agent is sodium pyrophosphate.
12. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein the anti-caking agent is added in a weight ratio is 1:1000 relative to LiOH, and wherein the anti-caking agent is sodium silicoaluminate.
13. The method for preparing lithium hydroxide monohydrate according to claim 3, wherein the anti-caking agent is added in a weight ratio of between 1:500 and 1:800 relative to LiOH, and wherein the anti-caking agent is trimeric sodium phosphate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106028943A CN102020294B (en) | 2010-12-23 | 2010-12-23 | Lithium hydroxide monohydrate and preparation method thereof |
| CN201010602894.3 | 2010-12-23 | ||
| PCT/CN2011/076973 WO2012083677A1 (en) | 2010-12-23 | 2011-07-08 | Dust free lithium hydroxide monohydrate and preparation method therefor |
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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 |
| WO2019220003A1 (en) | 2018-05-18 | 2019-11-21 | Outotec (Finland) Oy | Method for recovering lithium hydroxide |
| 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 |
| 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 |
| 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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| US6921522B2 (en) * | 1998-07-16 | 2005-07-26 | Chemetall Foote Corporation | Production of lithium compounds directly from lithium containing brines |
| US5948736A (en) * | 1998-08-25 | 1999-09-07 | Toxco, Inc. | Dust free lithium hydroxide |
| CN1229059A (en) * | 1999-03-05 | 1999-09-22 | 四川省绵阳锂盐厂 | Technology for producing single water lithium hydroxide using spodumene |
| US6653262B2 (en) * | 2001-12-27 | 2003-11-25 | Toxco, Inc. | Dust free lithium hydroxide |
| CN1226189C (en) * | 2003-03-26 | 2005-11-09 | 邓月金 | Method for preparing lithium compound from lithium metasilicate mixed salt |
| US8168146B2 (en) * | 2006-11-08 | 2012-05-01 | The Lubrizol Corporation | Process for preparing high concentration dispersions of lithium hydroxide monohydrate and of anhydrous lithium hydroxide oils |
| CN100455512C (en) * | 2007-12-28 | 2009-01-28 | 四川天齐锂业股份有限公司 | Method for preparing battery-stage monohydrate lithium hydroxide |
| 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 |
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| CA2822196A1 (en) | 2012-06-28 |
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| CN102020294B (en) | 2012-04-25 |
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