WO2012083677A1 - Dust free lithium hydroxide monohydrate and preparation method therefor - Google Patents

Dust free lithium hydroxide monohydrate and preparation method therefor Download PDF

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Publication number
WO2012083677A1
WO2012083677A1 PCT/CN2011/076973 CN2011076973W WO2012083677A1 WO 2012083677 A1 WO2012083677 A1 WO 2012083677A1 CN 2011076973 W CN2011076973 W CN 2011076973W WO 2012083677 A1 WO2012083677 A1 WO 2012083677A1
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WIPO (PCT)
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sodium
lithium hydroxide
hydroxide monohydrate
lioh
caking agent
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PCT/CN2011/076973
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French (fr)
Chinese (zh)
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姚开林
金鹏
霍立明
何东利
何开茂
彭宗惠
涂明江
杨柳
江虎成
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雅安华汇锂业科技材料有限公司
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Priority to CA2822196A priority Critical patent/CA2822196C/en
Publication of WO2012083677A1 publication Critical patent/WO2012083677A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides

Definitions

  • the present invention relates to a dust-free grade lithium hydroxide monohydrate and a preparation method thereof, and belongs to the technical field of lithium hydroxide preparation. Background technique
  • Lithium hydroxide monohydrate ( ⁇ 2 0) is widely used in the manufacture of high-grade lithium-based greases. It is currently the largest consumer of ⁇ 2 0. Li-based greases produced by LiOH 0 are suitable for a wide temperature range (- 50 ° C ⁇ +300 ° C;), good fire performance, difficult to oxidize, multiple heating _ cooling _ heating cycle stability, long service life, strong water resistance.
  • ⁇ 20 is also widely used in the fields of chemical industry, national defense, and battery. Alkaline battery additives in the battery industry can extend their life and increase their storage capacity. It can absorb radioisotopes as an ion exchange resin in national defense and can be used as a heat carrier for nuclear reactors and as a protective agent for metal surfaces.
  • ⁇ 20 can be used for air purification in submarines, breathing masks for pilots.
  • ⁇ 2 0 can also be used as a water purifying agent, an emulsifier for the production of porous concrete, a special optical glass raw material, and a raw material for synthesizing vitamin A and many other lithium salt products.
  • the preparation methods of LiOH H 2 0 mainly include:
  • the lithium-containing ore and limestone are mixed and ground in a certain mass ratio.
  • the ground slurry is then sent to a rotary kiln for calcination, and the CaO produced by the decomposition of calcium carbonate reacts with the lithium ore to form LiOH.
  • the shortcomings of high energy consumption, high material flow, high cost and difficult product quality it is rarely used.
  • the ⁇ -spodumene concentrate is calcined in a rotary kiln at 1050 ° C to 1100 ° C to be converted into ⁇ -spodumene, and a certain amount of Na 2 C0 3 is added and uniformly mixed, and the temperature is leached at 200 ° C.
  • the soluble LiHC0 3 is formed by passing through C0 2 , and the residue is removed by filtration, and then the refined lime milk is added in a stoichiometric ratio, and the reaction liquid is concentrated and crystallized to obtain ⁇ 20 .
  • the brine is concentrated to a Li content of 5% to 7% (35% to 44% in terms of LiCl), and after filtration, the pH is adjusted to 10.5 to 1.5, and the calcium and magnesium ions in the brine are removed by precipitation to obtain a purified brine (the main component is LiCl), then the refined brine is electrolyzed in a special electrolytic cell as an electrolyte, the anolyte is refined brine, the catholyte is water or LiOH solution; there is a cation selective permeation between the anolyte and the catholyte Membrane (e.g., perfluorosulfonic acid membrane Rf-S0 3 H, perfluorocarboxylic acid membrane Rf-COOH, etc.), the cation can pass, and the anion is blocked from passing.
  • a cation selective permeation between the anolyte and the catholyte Membrane (e.g., perfluorosulfonic acid membrane R
  • Li + can migrate through the membrane to the cathode and convert to LiOH.
  • the H 2 and Cl 2 produced by the reaction can be used as a by-product to manufacture HC1.
  • a LiOH solution having a concentration of about 14% can be obtained at the cathode, and the crystal is dried to obtain a LiOH product.
  • this method has high energy consumption, high cost, and great environmental impact.
  • a fluorine-containing cation exchange resin for example, C 2 H 4 and CF 2
  • LiOH is prepared by ion-exchange membrane electrolysis, which not only has high Li recovery rate (nearly 100%), no secondary pollution, but also has high purity (>99%), which can be directly used to produce lithium lubricant.
  • the method requires very high content of impurity ions in the refined brine: the total concentration of Na + and K + is below 5%, and the total amount of Ca 2+ and Mg 2+ is not more than 0.004%.
  • the ion film is expensive and difficult to maintain, and the production cost of preparing LiOH is relatively increased.
  • the method produces lithium hydroxide by using 10% sodium aluminate as a raw material, and carbonizing and decomposing 40% of C0 2 to obtain Al(OH) 3 , and adding aluminum to lithium by weight ratio of 13 ⁇ 15 to boron.
  • brine containing 0.13% Li
  • pH 6.8 ⁇ 7.0 is controlled, temperature is 90 °C
  • Al(OH) 3 can form stable aluminum lithium compound with Li + in brine (LiCl'2Al(OH nH 2 0) Precipitation, lithium precipitation rate of 95%.
  • the obtained aluminum lithium precipitate is calcined in the presence of a neutral salt (such as NaN0 3 , NaCl, etc.) at 120 ° C ⁇ 130 ° C for 20 min ⁇ 30 min, which is decomposed into ⁇ 1 ( ⁇ ) 3 and soluble lithium salt, hot water Leaching to separate the aluminum lithium in the precipitate.
  • a neutral salt such as NaN0 3 , NaCl, etc.
  • the leachate is passed through an exchange column containing a strongly acidic cation exchange resin, and the cations such as Li + and Mg 2+ in the solution are replaced in an exchange column, and then eluted with 1% to 20% caustic solution.
  • the impurity ions such as Mg 2+ and Ca 2+ are precipitated in the exchange column, and Li + forms LiOH to flow out with the solution; or the leachate is passed through an exchange column containing a strong basic anion exchange resin in the solution.
  • the LiCl is converted to LiOH and flows out with the solution, and impurity ions such as Mg 2+ and Ca 2+ are precipitated and left in the exchange column to be separated.
  • the concentration of LiOH solution obtained by the method is about 6%, and the recovery rate of lithium is above 90%.
  • the obtained LiOH solution was concentrated by evaporation and dried by crystallization to obtain a LiOH product.
  • the soda ash and aluminum hydroxide recovered from the carbonized liquid are calcined at 900 ° C, and the sodium aluminate obtained after leaching can be recycled.
  • the disadvantage of this method for industrial scale production is that the obtained aluminum lithium precipitate is a colloid, the solid weight is only about 10%, the average particle is only ⁇ , it is difficult to filter and the process is complicated, and the energy consumption is high.
  • the brine is made of boron, evaporated to 50% of water, calcined at 700 ° C for 2 h, the magnesium chloride in the brine is pyrolyzed to magnesium oxide, the decomposition rate is 93%, and then leached with water, the leachate (containing 0.14% of lithium) milk of lime and soda ash removing calcium and magnesium ions, Na 3 P0 4 were added precipitated Li 3 P0 4. Filtration, the Li 3 P0 4 precipitate is mixed with CaO and A1 2 3 3 in a ratio of 1:6: 2, and calcined in an electric resistance furnace at 2300 ° C for 2 h, and then the calcined mixture is used at 85 ° C to 95 ° C.
  • the hot water is leached, filtered, and the filtrate is concentrated by evaporation, crystallized, and dried to obtain a LiOH product.
  • the method has the advantages that the resources such as lithium magnesium can be comprehensively utilized, and the chemical raw materials are required to be small; the calcination can remove impurities such as boron and magnesium, and improve the purity of lithium hydroxide.
  • the disadvantages are: The use of magnesium makes the process complex, the equipment is seriously corroded, the amount of evaporated water is large, and the energy consumption is high.
  • Patent No. ZL 200710051016.5 provides a method for preparing battery-grade lithium hydroxide monohydrate.
  • the method comprises the following steps: evaporating and concentrating the lithium sulphate leaching solution, adding NaOH, filtering and removing impurities such as Fe, Ca, Mn, and then freezing to - After 5 ⁇ 3 °C, Na 2 S (V 10H 2 O was separated by filtration, and then the filtrate was concentrated by evaporation to crystallize the crude ⁇ 2 0, and the crude ⁇ 2 0 was redissolved and transferred to the crude ⁇ 2 Adding the refined preparation to the 0 heavy solution, in addition to Na, cooling and crystallizing and separating, the solid is wet ⁇ 2 0, and then dried to obtain ⁇ 2 0 product.
  • the lithium silicate conversion method is to co-melt the obtained lithium carbonate with silicic acid to form lithium silicate, and the lithium silicate is hydrolyzed to produce lithium hydroxide; the lithium sulfate conversion method first converts lithium in the salt lake brine into lithium sulfate. Reuse lithium sulphate and barium hydroxide The reaction produces lithium hydroxide.
  • the lithium silicate method and the lithium sulphate method for preparing lithium hydroxide are still immature and are under study.
  • the ⁇ 20 prepared by the above method has a problem of flying nose dust flying in use, and as the environmental awareness of people increases, higher requirements are placed on the working environment, and the problem of dust flying is imminent.
  • the undried wet ⁇ ⁇ 20 can solve the problem of dust flying
  • the wet ⁇ 20 has a knot.
  • the knot will appear, and it needs to be tapped into small pieces and then used for feeding. If it is not used for 3-4 days, it will become a plate with a high hardness and it is difficult to use. If it is more than 4 days, it is difficult to knock with a hammer and it cannot be used. Therefore, the procurement and production requirements are high, which seriously affects the use. Therefore, solving the problem of the knot of the wet ⁇ ⁇ 20 and the problem of the dust flying of the ⁇ ⁇ 20 has raised new issues in the field.
  • the technical problem to be solved by the present invention is that there is a problem of compaction of the existing wet ⁇ ⁇ 20, and there is a problem of dust flying in the dry ⁇ ⁇ 20 , and a new ⁇ 2 0 is provided, that is, a dust-free, non-boarding list.
  • Lithium hydroxide in water Lithium hydroxide in water.
  • the technical solution of the present invention is:
  • the lithium hydroxide monohydrate of the present invention is a loose granular wet product. Can be stored for 3-5 months without squashing, still retain loose particles.
  • the lithium hydroxide monohydrate is a loose granular wet product, wherein the moisture content is 3.5%, and the surface of the lithium hydroxide monohydrate is coated with a trace amount of an anti-caking agent, and the anti-caking agent is sodium dodecyl sulfate.
  • the anti-caking agent is sodium dodecyl sulfate.
  • the dust-free lithium hydroxide monohydrate of the present invention is prepared by the following method:
  • step (2) Evaporate the LiOH solution obtained in step (1) until the liquid-solid ratio is 1:0.8 ⁇ 1.5, add a small amount of anti-caking agent, stir evenly, separate and wash to obtain dust-free industrial grade ⁇ 2 0 product, vacuum
  • the sealed package is not tied for several months.
  • the temperature at which the anti-caking agent is added is preferably 90-100 ° C, and when the temperature is lowered to 90 ° C or lower, the S0 4 2 - content of the obtained wet product is extremely high.
  • step (1) controls S0 4 2 agricultural degree 8 g/l, and controls Na 2 0 concentration 2 g/l, CaO concentration 0.01 g/l; (2) When the anti-caking agent is added, the LiOH solution is evaporated to a liquid-to-solid ratio of 1:0.8 to 1.1.
  • the effect of controlling the liquid-solid ratio of evaporation is mainly used as a control means for the end point of evaporation.
  • the liquid-solid ratio is too high, and the evaporation end point is too advanced, which affects the yield and crystallization effect, and the crystal form is poor. If the liquid-solid ratio is too low, the evaporation end point will be too high, and the concentration of the liquid will be too high, which will make the impurities in the product higher.
  • Industrial products have higher levels of impurities than battery-grade products, so the concentration of liquid at the end of the evaporation can be higher than the concentration of the liquid at the end of the production of the battery-grade product, that is, the liquid-solid concentration of the liquid at the end of the production of industrial grade products.
  • the ratio may be less than the liquid to solid ratio of the battery level production evaporation end point liquid.
  • the anti-caking agent of the present invention may be: a sodium salt or a potassium salt such as sodium lauryl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, Or methylpentanol, triethylhexylphosphoric acid, cellulose derivatives, and the like.
  • a sodium salt or a potassium salt such as sodium lauryl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, Or methylpentanol, triethylhexylphosphoric acid, cellulose derivatives, and the like.
  • an insoluble anti-caking agent such as sodium aluminosilicate, tricalcium phosphate, amorphous silica or the like.
  • the insoluble anti-caking agent has a very small solubility, and the mixing effect in the slurry is poor, and its use amount is relatively large, which leads to an excessively high impurity of the product, so that the insoluble anti-caking agent is preferably not used.
  • the production environment of lithium hydroxide monohydrate is an inorganic salt system. According to the principle of similar compatibility of chemical substances, it is preferable not to use organic substances in the selection of anti-caking agents.
  • the LiOH solution in the step (1) can be prepared by using the prior art, or the crude ⁇ 2 0 is dissolved in water to purify and remove impurities to obtain a LiOH solution.
  • Lithium ore and limestone calcined to form LiOH which is obtained by impurity removal; ⁇ -spodumene is mixed with Na 2 C0 3 Evenly, the temperature is leached at 200 ° C, the soluble LiHC0 3 is formed by adding C0 2 , the refined lime milk is added according to the stoichiometric ratio, and the residue is obtained after the reaction; the lime milk and the lithium carbonate are causticized to obtain a LiOH solution; The brine is obtained by LiOH solution; the Li 2 SO 4 solution is electrolyzed to obtain LiOH solution; the sodium aluminate is decomposed by C0 2 carbonization to obtain Al(OH) 3 , which reacts with the brine to form a stable aluminum lithium compound (LiCl'2Al(OH) 3 'nH 2 0) Precipitation, calcination in the presence of a neutral salt (such as NaN0 3 , NaCl, etc.), which is decomposed into ⁇ 1(
  • the key point of the present invention is that a small amount of an additive and an anti-caking agent which do not affect the quality of the ⁇ 20 product are added during the precipitation of LiOH, and the precipitation process is regulated, so that the precipitated wet product ⁇ 20 is not plated during storage. Avoid the problem of dust flying after drying.
  • deionized water is used as much as possible during the formulation and rinsing process.
  • the invention has the advantages of simple production process, easy operation, less equipment investment, low product cost, high lithium recovery rate, stable product quality, and no flaws in the product, and the dust-free grade ⁇ 2 0 product completely produced. It can meet the quality needs and environmental requirements of the downstream industry.
  • the filtrate was a purified LiOH solution; the Li 2 0 concentration of 72 g/l LiOH solution, S0 4 2 agricultural degree 8g / l, and control Na 2 0 concentration 2g / l, CaO concentration of 0.01g / l.
  • the preparation process was the same as in Example 1, except that the amount of the anti-caking agent used and the type of the anti-caking agent were different. The specific results are shown in Table 1.
  • the crude product adding deionized water, stirring to completely dissolve it, and making the concentration of Li 2 0 in the solution 70g/L, separating and filtering, the filtrate is LiOH pure liquid; wherein the concentration of Li 2 0 is 70 g / l LiOH solution, S0 4 2 agricultural degree 12g / l, and control Na 2 0 concentration 5g / l, CaO concentration 0.06g / l.
  • the LiOH solution obtained in the step (1) is evaporated to a liquid-solid ratio of 1:1.2, the anti-caking agent is added, the mixture is evenly stirred, and the temperature of the material is maintained at 90°, and the solid obtained by separation and washing is industrial-grade dust-free ⁇ 2 0 .
  • Table 2 The condition of the tube after vacuum packaging is shown in Table 2.

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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 LiOH•H2O in view of the problems of hardening of wet LiOH•H2O and dusting of dry LiOH•H2O 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 LiOH•H2O, which does not harden in vacuum sealed package in 3-5 months.

Description

无尘级单水氢氧化锂及其制备方法  Dust-free grade lithium hydroxide monohydrate and preparation method thereof
技术领域 本发明涉及一种无尘级单水氢氧化锂及其制备方法，属于氢氧化锂制备技术领域。 背景技术 TECHNICAL FIELD The present invention relates to a dust-free grade lithium hydroxide monohydrate and a preparation method thereof, and belongs to the technical field of lithium hydroxide preparation. Background technique
单水氢氧化锂 （ ΟΗ·Η20) 的用途广泛， 制造高级锂基润滑脂是目前 ΟΗ·Η20 消费量最大的领域， LiOH 0生产的锂基润滑脂， 适用温度范围宽（-50°C〜+300°C；)、 防火性能好、 难氧化、 多次加热_冷却 _加热循环时性能稳定， 使用寿命长， 抗水性 强。 此外， ΟΗ·Η20在化工、 国防、 电池等领域也有广泛应用。 在电池工业中用于碱 性蓄电池添加剂可以延长其寿命， 增加蓄电量。 在国防上作为离子交换树脂可以吸收 放射性同位素， 可用作核反应堆的热载体和金属表面的保护剂。 在航空航天方面， ΟΗ·Η20可用于潜水艇中空气净化， 飞行员的呼吸罩。 ΟΗ·Η20还可作为水净化剂、 生产多孔混凝土的乳化剂、特种光学玻璃原料以及合成维生素 A和其它很多锂盐产品 的原料。 Lithium hydroxide monohydrate (ΟΗ·Η 2 0) is widely used in the manufacture of high-grade lithium-based greases. It is currently the largest consumer of ΟΗ·Η 2 0. Li-based greases produced by LiOH 0 are suitable for a wide temperature range (- 50 ° C ~ +300 ° C;), good fire performance, difficult to oxidize, multiple heating _ cooling _ heating cycle stability, long service life, strong water resistance. In addition, ΟΗ·Η 20 is also widely used in the fields of chemical industry, national defense, and battery. Alkaline battery additives in the battery industry can extend their life and increase their storage capacity. It can absorb radioisotopes as an ion exchange resin in national defense and can be used as a heat carrier for nuclear reactors and as a protective agent for metal surfaces. In aerospace, ΟΗ·Η 20 can be used for air purification in submarines, breathing masks for pilots. ΟΗ·Η 2 0 can also be used as a water purifying agent, an emulsifier for the production of porous concrete, a special optical glass raw material, and a raw material for synthesizing vitamin A and many other lithium salt products.
LiOH H20 的制备方法主要有： The preparation methods of LiOH H 2 0 mainly include:
1、 石灰石焙烧法  1. Limestone roasting method
将含锂矿石与石灰石按一定质量比混合、 磨细。 然后将磨好的料浆送入回转窑内 煅烧， 碳酸钙分解产生的 CaO与锂矿石反应生成 LiOH。 但由于此工艺能耗高、 物料流 通量大、 成本高、 产品质量难以提高等缺点， 现已很少采用。  The lithium-containing ore and limestone are mixed and ground in a certain mass ratio. The ground slurry is then sent to a rotary kiln for calcination, and the CaO produced by the decomposition of calcium carbonate reacts with the lithium ore to form LiOH. However, due to the shortcomings of high energy consumption, high material flow, high cost and difficult product quality, it is rarely used.
2、 β-锂辉石碳酸钠加压浸取法  2, β-spodumene sodium carbonate pressure leaching method
将 α-锂辉石精矿在 1050°C〜1100°C的回转窑中焙烧， 使其转化为 β-锂辉石， 加入 一定量的 Na2C03混合均匀， 加温在 200°C浸出， 通入 C02生成可溶性的 LiHC03， 过滤 除去残渣， 然后按化学计量比加入精制石灰乳， 反应液浓缩结晶得到 ΟΗ·Η20。 The α-spodumene concentrate is calcined in a rotary kiln at 1050 ° C to 1100 ° C to be converted into β-spodumene, and a certain amount of Na 2 C0 3 is added and uniformly mixed, and the temperature is leached at 200 ° C. The soluble LiHC0 3 is formed by passing through C0 2 , and the residue is removed by filtration, and then the refined lime milk is added in a stoichiometric ratio, and the reaction liquid is concentrated and crystallized to obtain ΟΗ·Η 20 .
3、 碳酸锂苛化法  3, lithium carbonate causticization
将精制石灰乳与碳酸锂按一定的比例混合， 调节一定的苛化液浓度， 加热至沸腾 并强力搅拌， 苛化反应如下：  Mix the refined lime milk with lithium carbonate in a certain ratio, adjust the concentration of caustic solution, heat to boiling and stir vigorously. The causticization reaction is as follows:
Ca(OH)2 + Li2C03 = CaC03|+ 2LiOH 反应可得到浓度约 3.5%的 LiOH溶液。 除去不溶性的残渣 (主要是 CaC03)， 分离后 将母液减压浓缩、 结晶而得到单水氢氧化锂。 单水氢氧化锂在 130°C〜140°C干燥， 再 在 150°C〜180°C下减压加热， 制得无水 LiOH。 碳酸锂苛化法生产氢氧化锂是目前国内 外特别是国外生产氢氧化锂的主要方法。 但此生产工艺流程长， 设备投资较多， 成本 高， 且主要原料为碳酸锂， 其价格的高低直接影响到单水氢氧化锂的成本。 Ca(OH) 2 + Li 2 C0 3 = CaC0 3 |+ 2LiOH The reaction gave a LiOH solution having a concentration of about 3.5%. The insoluble residue (mainly CaC0 3 ) was removed, and after separation, the mother liquid was concentrated under reduced pressure and crystallized to obtain lithium hydroxide monohydrate. Lithium hydroxide monohydrate is dried at 130 ° C to 140 ° C, and further heated under reduced pressure at 150 ° C to 180 ° C to obtain anhydrous LiOH. The production of lithium hydroxide by the causticization process of lithium carbonate is the main method for producing lithium hydroxide at home and abroad, especially abroad. However, this production process is long, the equipment investment is high, the cost is high, and the main raw material is lithium carbonate, and the price thereof directly affects the cost of lithium hydroxide monohydrate.
4、 电解精制卤水  4, electrolytically refined brine
将卤水浓缩到含 Li为 5%〜7% (以 LiCl计为 35%〜44%)， 过滤后调 pH10.5〜l 1.5， 沉 淀除去卤水中的钙镁离子，得到精制卤水 (主要成分是 LiCl)，然后将精制卤水作为电解 液放在特制的电解槽中电解， 阳极电解液为精制卤水， 阴极电解液为水或 LiOH溶液； 在阳极电解液和阴极电解液之间有一阳离子选择性渗透膜 (如全氟磺酸膜 Rf— S03H、 全氟羧酸膜 Rf— COOH等） ， 阳离子可以通过， 而阴离子被阻挡而不能通过。 电解时， Li+可以透过膜迁移到阴极转化为 LiOH。 反应产生的 H2和 Cl2可作为副产品制造 HC1。 最终在阴极可得到浓度约为 14%的 LiOH溶液， 结晶干燥， 即得 LiOH产品。但此方法能 耗大， 成本高， 对环境影响较大。 The brine is concentrated to a Li content of 5% to 7% (35% to 44% in terms of LiCl), and after filtration, the pH is adjusted to 10.5 to 1.5, and the calcium and magnesium ions in the brine are removed by precipitation to obtain a purified brine (the main component is LiCl), then the refined brine is electrolyzed in a special electrolytic cell as an electrolyte, the anolyte is refined brine, the catholyte is water or LiOH solution; there is a cation selective permeation between the anolyte and the catholyte Membrane (e.g., perfluorosulfonic acid membrane Rf-S0 3 H, perfluorocarboxylic acid membrane Rf-COOH, etc.), the cation can pass, and the anion is blocked from passing. During electrolysis, Li + can migrate through the membrane to the cathode and convert to LiOH. The H 2 and Cl 2 produced by the reaction can be used as a by-product to manufacture HC1. Finally, a LiOH solution having a concentration of about 14% can be obtained at the cathode, and the crystal is dried to obtain a LiOH product. However, this method has high energy consumption, high cost, and great environmental impact.
5、 电解 Li2S04溶液 5, electrolytic Li 2 S0 4 solution
将 Li2S04溶液作为阳极液， 水作为阴极液放于膜电解槽装置中进行电解， 其中阳 极电解液和阴极电解液之间用含氟阳离子交换树脂 (；如 C2H4和 CF2=CFOCCF2)3COCF3 的异分子聚合物） 隔开， 控制电压为 6V， 电流密度为 100A/dm2， 在阴极可获得质量浓 度约为 10%的 LiOH溶液， 同时在阳极可获得 H2S04溶液。 离子膜电解法制备 LiOH, 不 仅 Li回收率高 (近 100%) ， 无二次污染， 而且制得的产品纯度高(>99%)， 可直接用来生 产锂润滑剂。但本方法对精制卤水杂质离子的含量要求非常高: Na+和 K+的总浓度在 5% 以下， Ca2+和 Mg2+的总量不超过 0.004%。 另外， 离子膜价格昂贵、 不易维护， 相对提 高了制备 LiOH的生产成本。 The Li 2 S0 4 solution is used as an anolyte, and water is used as a catholyte in a membrane electrolyzer device for electrolysis, wherein a fluorine-containing cation exchange resin (for example, C 2 H 4 and CF 2 ) is used between the anolyte and the catholyte. =CFOCCF 2 ) 3COCF 3 isomerized polymer) separated, control voltage is 6V, current density is 100A/dm 2 , LiOH solution with mass concentration of about 10% can be obtained at the cathode, and H 2 S0 can be obtained at the anode. 4 solution. LiOH is prepared by ion-exchange membrane electrolysis, which not only has high Li recovery rate (nearly 100%), no secondary pollution, but also has high purity (>99%), which can be directly used to produce lithium lubricant. However, the method requires very high content of impurity ions in the refined brine: the total concentration of Na + and K + is below 5%, and the total amount of Ca 2+ and Mg 2+ is not more than 0.004%. In addition, the ion film is expensive and difficult to maintain, and the production cost of preparing LiOH is relatively increased.
6、 铝酸盐锂沉淀法  6, lithium aluminate precipitation method
本方法生产氢氧化锂是以浓度 10%的铝酸钠为原料，用浓度为 40%的 C02碳化分解 制得 Al(OH)3， 按铝锂重量比 13〜15加入到提硼后的卤水 (含 Li0.13%)中， 控制 pH6.8〜 7.0， 温度 90°C， Al(OH)3可与卤水中的 Li+生成稳定的铝锂化合物 (LiCl'2Al(OH nH20) 沉淀， 锂的沉淀率达 95%。 将得到的铝锂沉淀物在中性盐（ 如 NaN03， NaCl 等） 存在 下于 120°C〜130°C煅烧 20min〜30min， 使其分解为 Α1(ΟΗ)3和可溶性锂盐， 热水浸取， 使沉淀物中的铝锂分离。 将浸取液流过装有强酸性阳离子交换树脂的交换柱， 溶液中 的 Li+、 Mg2+等阳离子被置换留在交换柱中， 然后用 1%〜20%的苛性碱液洗脱， Mg2+、 Ca2+等杂质离子生成氢氧化物沉淀留在交换柱中， Li+生成 LiOH随溶液流出； 或者将浸 取液流过装有强碱性阴离子交换树脂的交换柱， 溶液中的 LiCl被转换为 LiOH随溶液流 出， Mg2+、 Ca2+等杂质离子被沉淀留在交换柱中被分离。 本方法得到的 LiOH溶液浓度 为 6%左右， 锂的回收率在 90%以上。 将得到的 LiOH溶液蒸发浓缩、 结晶干燥， 即得 LiOH产品。 从碳化液中回收的纯碱和氢氧化铝在 900°C煅烧， 浸取后得到的铝酸钠可 以循环利用。 该方法用于工业规模生产时的缺点是所得的铝锂沉淀物为胶体， 固体重 量只占 10%左右， 平均颗粒仅 Ιμιη, 不易过滤并且工艺流程复杂， 能耗高。 The method produces lithium hydroxide by using 10% sodium aluminate as a raw material, and carbonizing and decomposing 40% of C0 2 to obtain Al(OH) 3 , and adding aluminum to lithium by weight ratio of 13~15 to boron. In brine (containing 0.13% Li), pH 6.8~7.0 is controlled, temperature is 90 °C, Al(OH) 3 can form stable aluminum lithium compound with Li + in brine (LiCl'2Al(OH nH 2 0) Precipitation, lithium precipitation rate of 95%. The obtained aluminum lithium precipitate is calcined in the presence of a neutral salt (such as NaN0 3 , NaCl, etc.) at 120 ° C ~ 130 ° C for 20 min ~ 30 min, which is decomposed into Α 1 (ΟΗ) 3 and soluble lithium salt, hot water Leaching to separate the aluminum lithium in the precipitate. The leachate is passed through an exchange column containing a strongly acidic cation exchange resin, and the cations such as Li + and Mg 2+ in the solution are replaced in an exchange column, and then eluted with 1% to 20% caustic solution. The impurity ions such as Mg 2+ and Ca 2+ are precipitated in the exchange column, and Li + forms LiOH to flow out with the solution; or the leachate is passed through an exchange column containing a strong basic anion exchange resin in the solution. The LiCl is converted to LiOH and flows out with the solution, and impurity ions such as Mg 2+ and Ca 2+ are precipitated and left in the exchange column to be separated. The concentration of LiOH solution obtained by the method is about 6%, and the recovery rate of lithium is above 90%. The obtained LiOH solution was concentrated by evaporation and dried by crystallization to obtain a LiOH product. The soda ash and aluminum hydroxide recovered from the carbonized liquid are calcined at 900 ° C, and the sodium aluminate obtained after leaching can be recycled. The disadvantage of this method for industrial scale production is that the obtained aluminum lithium precipitate is a colloid, the solid weight is only about 10%, the average particle is only Ιμιη, it is difficult to filter and the process is complicated, and the energy consumption is high.
7、 煅烧法  7, calcination method
将卤水提硼，蒸发去水 50%，在 700°C下煅烧 2h， 卤水中的氯化镁热解变成氧化镁， 分解率达 93%， 再用水浸取， 浸取液 (含锂 0.14 %) 加石灰乳和纯碱除去钙镁离子， 加 入 Na3P04沉淀出 Li3P04。过滤，将 Li3P04沉淀与 CaO和 A1203以 1： 6： 2的比例混合磨细， 于电阻炉中保持 2300°C焙烧 2h， 然后把煅烧混合物用 85 °C〜95 °C的热水浸出， 过滤， 滤液经蒸发浓缩、 结晶、 干燥， 可得 LiOH产品。 该方法的优点是:锂镁等资源可综合 利用， 需化工原料少； 煅烧可以去除硼镁等杂质， 提高了氢氧化锂的纯度。 缺点是： 镁的使用使得工艺流程复杂， 设备腐蚀严重， 蒸发水量大， 能耗高。 The brine is made of boron, evaporated to 50% of water, calcined at 700 ° C for 2 h, the magnesium chloride in the brine is pyrolyzed to magnesium oxide, the decomposition rate is 93%, and then leached with water, the leachate (containing 0.14% of lithium) milk of lime and soda ash removing calcium and magnesium ions, Na 3 P0 4 were added precipitated Li 3 P0 4. Filtration, the Li 3 P0 4 precipitate is mixed with CaO and A1 2 3 3 in a ratio of 1:6: 2, and calcined in an electric resistance furnace at 2300 ° C for 2 h, and then the calcined mixture is used at 85 ° C to 95 ° C. The hot water is leached, filtered, and the filtrate is concentrated by evaporation, crystallized, and dried to obtain a LiOH product. The method has the advantages that the resources such as lithium magnesium can be comprehensively utilized, and the chemical raw materials are required to be small; the calcination can remove impurities such as boron and magnesium, and improve the purity of lithium hydroxide. The disadvantages are: The use of magnesium makes the process complex, the equipment is seriously corroded, the amount of evaporated water is large, and the energy consumption is high.
8、 专利号为 ZL 200710051016.5提供了一种电池级单水氢氧化锂的制备方法 该方法是将硫酸锂浸出液适当蒸发浓缩， 加入 NaOH反应， 过滤除去 Fe、 Ca、 Mn 等杂质， 然后冷冻到 -5±3 °C后， 过滤分离出 Na2S(V 10H2O， 然后将滤液蒸发浓缩结晶 出粗 ΟΗ·Η20， 将粗 ΟΗ·Η20重溶， 并向粗 ΟΗ·Η20重溶液中加入精制剂除 Na， 冷 却结晶过滤分离， 固体为湿 ΟΗ·Η20， 再经干燥制得 ΟΗ·Η20产品。 8. Patent No. ZL 200710051016.5 provides a method for preparing battery-grade lithium hydroxide monohydrate. The method comprises the following steps: evaporating and concentrating the lithium sulphate leaching solution, adding NaOH, filtering and removing impurities such as Fe, Ca, Mn, and then freezing to - After 5±3 °C, Na 2 S (V 10H 2 O was separated by filtration, and then the filtrate was concentrated by evaporation to crystallize the crude ΟΗ·Η 2 0, and the crude ΟΗ·Η 2 0 was redissolved and transferred to the crude Η·Η 2 Adding the refined preparation to the 0 heavy solution, in addition to Na, cooling and crystallizing and separating, the solid is wet ΟΗ·Η 2 0, and then dried to obtain ΟΗ·Η 2 0 product.
9、 硅酸锂转化法  9, lithium silicate conversion method
硅酸锂转化法是将制得的碳酸锂与硅酸共熔， 生成硅酸锂， 硅酸锂水解， 产生氢 氧化锂； 硫酸锂转化法是先把盐湖卤水中的锂转化为硫酸锂， 再用硫酸锂和氢氧化钡 反应， 产生氢氧化锂。 目前， 硅酸锂法和硫酸锂法制备氢氧化锂技术还不成熟， 正在 研究当中。 The lithium silicate conversion method is to co-melt the obtained lithium carbonate with silicic acid to form lithium silicate, and the lithium silicate is hydrolyzed to produce lithium hydroxide; the lithium sulfate conversion method first converts lithium in the salt lake brine into lithium sulfate. Reuse lithium sulphate and barium hydroxide The reaction produces lithium hydroxide. At present, the lithium silicate method and the lithium sulphate method for preparing lithium hydroxide are still immature and are under study.
上述方法制备的 ΟΗ·Η20在使用中由于存在剌鼻粉尘飞扬的问题，随着人们环保 意识的增强， 对工作环境提出了更高要求， 粉尘飞扬问题迫在眉睫。 虽然未干燥的湿 ΟΗ·Η20能解决粉尘飞扬的问题， 但湿的 ΟΗ·Η20存在板结的情况。 使用过程中， 2 天未使用则出现板结现象， 需要敲打成小块后投料使用。 若 3-4天未使用， 则会变成硬 度很大的板块， 难以使用。 超过 4天， 则用铁锤都难以敲散， 不能使用。 因此对采购和 生产要求较高， 严重影响起使用。 因此， 解决湿 ΟΗ·Η20的板结问题和干 ΟΗ·Η20 的粉尘飞扬问题为本领域提出了新的课题。 The ΟΗ·Η 20 prepared by the above method has a problem of flying nose dust flying in use, and as the environmental awareness of people increases, higher requirements are placed on the working environment, and the problem of dust flying is imminent. Although the undried wet ΟΗ Η 20 can solve the problem of dust flying, the wet ΟΗ·Η 20 has a knot. During the use, if there is no use for 2 days, the knot will appear, and it needs to be tapped into small pieces and then used for feeding. If it is not used for 3-4 days, it will become a plate with a high hardness and it is difficult to use. If it is more than 4 days, it is difficult to knock with a hammer and it cannot be used. Therefore, the procurement and production requirements are high, which seriously affects the use. Therefore, solving the problem of the knot of the wet ΟΗ Η 20 and the problem of the dust flying of the ΟΗ Η 20 has raised new issues in the field.
发明内容 Summary of the invention
本发明所要解决的技术问题是针对现有湿 ΟΗ·Η20存在板结问题，干 ΟΗ·Η20 存在粉尘飞扬问题， 提供一种新的 ΟΗ·Η20， 即无尘、 不板结单水氢氧化锂。 The technical problem to be solved by the present invention is that there is a problem of compaction of the existing wet ΟΗ Η 20, and there is a problem of dust flying in the dry Η Η 20 , and a new ΟΗ·Η 2 0 is provided, that is, a dust-free, non-boarding list. Lithium hydroxide in water.
本发明的技术方案是： 本发明单水氢氧化锂是一种疏松的颗粒状湿品。 可以存放 3-5个月未板结， 仍然保持疏松状颗粒。  The technical solution of the present invention is: The lithium hydroxide monohydrate of the present invention is a loose granular wet product. Can be stored for 3-5 months without squashing, still retain loose particles.
所述单水氢氧化锂为疏松的颗粒状湿品， 其中， 水份含量 3.5%， 单水氢氧化锂 表面包裹微量的防板结剂， 所述防板结剂为十二烷基磺酸钠、 亚铁氰化钠、 亚铁氰 化钾、 六偏磷酸钠、 三聚磷酸钠、 焦磷酸钠、 十二醇硫酸钠、 聚丙烯酰胺、 甲基 戊醇、 三乙基己基磷酸或纤维素衍生物中的一种。 优选十二烷基磺酸钠、 六偏磷酸 钠、 亚铁氰化钾或亚铁氰化钠中的一种； 其中， 防板结剂的重量为 l〜10ppm。  The lithium hydroxide monohydrate is a loose granular wet product, wherein the moisture content is 3.5%, and the surface of the lithium hydroxide monohydrate is coated with a trace amount of an anti-caking agent, and the anti-caking agent is sodium dodecyl sulfate. Sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium decol sulfate, polyacrylamide, methylpentanol, triethylhexylphosphoric acid or cellulose One of them. Preferably, one of sodium dodecylsulfonate, sodium hexametaphosphate, potassium ferrocyanide or sodium ferrocyanide; wherein the weight of the anti-caking agent is from 1 to 10 ppm.
本发明无尘单水氢氧化锂是由以下方法制备：  The dust-free lithium hydroxide monohydrate of the present invention is prepared by the following method:
( 1 ) 制得 Li20浓度为 70±5g/l的 LiOH溶液， 其中， 控制 S04 2农度 15g/l; (1) obtaining a LiOH solution having a Li 2 0 concentration of 70±5 g/l, wherein, the S0 4 2 agricultural degree is controlled by 15 g/l;
(2) 将步骤 （1 ) 得到的 LiOH溶液蒸发至液固比为 1 :0.8〜1.5时加入微量防板 结剂， 搅拌均匀， 分离、 洗涤即得无尘工业级 ΟΗ·Η20产品， 真空密封包装几个月 不板结。 (2) Evaporate the LiOH solution obtained in step (1) until the liquid-solid ratio is 1:0.8~1.5, add a small amount of anti-caking agent, stir evenly, separate and wash to obtain dust-free industrial grade ΟΗ·Η 2 0 product, vacuum The sealed package is not tied for several months.
其中， 防板结剂加入时的温度优选 90-100°C， 温度降低至 90°C以下时， 所得湿品 的 S04 2—含量超高。 Among them, the temperature at which the anti-caking agent is added is preferably 90-100 ° C, and when the temperature is lowered to 90 ° C or lower, the S0 4 2 - content of the obtained wet product is extremely high.
其中， 其中， 所述防板结剂为十二烷基磺酸钠、 亚铁氰化钠、 亚铁氰化钾、 六 偏磷酸钠、 三聚磷酸钠、 焦磷酸钠、 十二醇硫酸钠、 聚丙烯酰胺、 甲基戊醇、 三 乙基己基磷酸或纤维素衍生物中的一种； 防板结剂的加入量为： 防板结剂的重量与 物料中 LiOH的重量比 =1 : 1000〜10000。 Wherein, the anti-caking agent is sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, six One of sodium metaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium decanoate, polyacrylamide, methylpentanol, triethylhexylphosphoric acid or cellulose derivative; the amount of anti-caking agent added is : The weight ratio of the anti-caking agent to the weight of LiOH in the material = 1: 1000~10000.
防板结剂的使用量过多高会引入新的杂质，造成产品杂质含量超标，产品不合格。 过低， 对防板结效果不明显。  If the amount of anti-caking agent is too high, new impurities will be introduced, resulting in excessive impurities in the product and unqualified products. Too low, the effect on the anti-caking is not obvious.
进一步地， 为了得到纯度更高的电池级的 ΟΗ·Η20， 步骤 （1 ) 控制 S04 2农度 8g/l， 并控制 Na20浓度 2g/l， CaO浓度 0.01g/l; 步骤（2)加入防板结剂时 LiOH 溶液蒸发至液固比体积比为 1 :0.8〜1.1。 Further, in order to obtain a higher-purity battery-grade ΟΗ·Η 2 0, step (1) controls S0 4 2 agricultural degree 8 g/l, and controls Na 2 0 concentration 2 g/l, CaO concentration 0.01 g/l; (2) When the anti-caking agent is added, the LiOH solution is evaporated to a liquid-to-solid ratio of 1:0.8 to 1.1.
控制蒸发液固比的作用主要是作为蒸发终点的控制手段。 液固比过高， 蒸发终点 过于提前， 影响产出率和结晶效果， 晶形差。 液固比过低， 蒸发终点退后， 使得料液 浓度过高， 会使得产品中的杂质偏高。  The effect of controlling the liquid-solid ratio of evaporation is mainly used as a control means for the end point of evaporation. The liquid-solid ratio is too high, and the evaporation end point is too advanced, which affects the yield and crystallization effect, and the crystal form is poor. If the liquid-solid ratio is too low, the evaporation end point will be too high, and the concentration of the liquid will be too high, which will make the impurities in the product higher.
工业级产品的杂质允许含量较电池级产品高， 所以蒸发终点时的料液浓度可以高 于电池级产品生产时蒸发终点料液的浓度， 也就是工业级产品生产时蒸发终点料液的 液固比可以小于电池级生产蒸发终点料液的液固比。  Industrial products have higher levels of impurities than battery-grade products, so the concentration of liquid at the end of the evaporation can be higher than the concentration of the liquid at the end of the production of the battery-grade product, that is, the liquid-solid concentration of the liquid at the end of the production of industrial grade products. The ratio may be less than the liquid to solid ratio of the battery level production evaporation end point liquid.
本发明所述防板结剂可以是： 钠盐或钾盐， 如十二烷基硫酸钠、 亚铁氰化钠、 亚 铁氰化钾、 六偏磷酸钠、 三聚磷酸钠、 焦磷酸钠、 或甲基戊醇、 三乙基己基磷酸、 纤维素衍生物等。  The anti-caking agent of the present invention may be: a sodium salt or a potassium salt such as sodium lauryl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, Or methylpentanol, triethylhexylphosphoric acid, cellulose derivatives, and the like.
优选的是溶解度较大防板结剂： 十二烷基磺酸钠、 六偏磷酸钠、 亚铁氰化钾、 亚 铁氰化钠中的一种。  Preferred is a more soluble anti-caking agent: one of sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide, and sodium ferrocyanide.
最好不使用的是： 不溶性防板结剂如硅铝酸钠、磷酸三钙、无定形二氧化硅等。 不溶性防板结剂由于其溶解度极小， 料浆中的混合效果差， 而且其使用量相 对较大， 这将导致产品的杂质超高， 所以不溶性防板结剂最好不要使用。 同时， 单水氢氧化锂生产环境是无机盐体系， 根据化学物质相似相溶原理， 所以， 在防 板结剂的选择上最好也不要使用有机物质。  It is preferable not to use: an insoluble anti-caking agent such as sodium aluminosilicate, tricalcium phosphate, amorphous silica or the like. The insoluble anti-caking agent has a very small solubility, and the mixing effect in the slurry is poor, and its use amount is relatively large, which leads to an excessively high impurity of the product, so that the insoluble anti-caking agent is preferably not used. At the same time, the production environment of lithium hydroxide monohydrate is an inorganic salt system. According to the principle of similar compatibility of chemical substances, it is preferable not to use organic substances in the selection of anti-caking agents.
其中步骤（ 1 )中的 LiOH溶液可以采用现有技术制备得到，或采用粗品 ΟΗ·Η20 溶于水精制除杂得到 LiOH溶液。 The LiOH solution in the step (1) can be prepared by using the prior art, or the crude ΟΗ·Η 2 0 is dissolved in water to purify and remove impurities to obtain a LiOH solution.
比如： 含锂矿石与石灰石煅烧反应生成 LiOH, 除杂得到； β-锂辉石与 Na2C03混 合均匀， 加温在 200°C浸出， 通入 C02生成可溶性的 LiHC03， 按化学计量比加入精制 石灰乳， 反应后除杂得到； 石灰乳与碳酸锂苛化反应得到 LiOH溶液； 电解精制卤水 得到 LiOH溶液； 电解 Li2S04 溶液得到 LiOH溶液； 铝酸钠用 C02碳化分解制得 Al(OH)3，与卤水反应生成稳定的铝锂化合物 (LiCl'2Al(OH)3'nH20) 沉淀，在中性盐 (； 如 NaN03 , NaCl 等） 存在下煅烧， 使其分解为 Α1(ΟΗ)3 和可溶性锂盐， 热水浸取， 过强 酸性阳离子交换树脂的交换柱除杂， Li+生成 LiOH随溶液流出； 硫酸锂加入 NaOH反 应， 过滤除去 Fe、 Ca、 Mn等杂质， 然后冷冻到 -5±3 °C后， 过滤分离出 Na2S( 10H2O， 然后将滤液蒸发浓缩结晶出粗 LiOH 0，将粗 LiOH 0重溶得到 LiOH溶液 ... ...等 等方法得到 Li20浓度为 70±5g/l的 LiOH溶液， 并除杂至 S04 2农度 8g/l， Na20浓度 ^2g/l, CaO浓度 0.01g/l。 For example: Lithium ore and limestone calcined to form LiOH, which is obtained by impurity removal; β-spodumene is mixed with Na 2 C0 3 Evenly, the temperature is leached at 200 ° C, the soluble LiHC0 3 is formed by adding C0 2 , the refined lime milk is added according to the stoichiometric ratio, and the residue is obtained after the reaction; the lime milk and the lithium carbonate are causticized to obtain a LiOH solution; The brine is obtained by LiOH solution; the Li 2 SO 4 solution is electrolyzed to obtain LiOH solution; the sodium aluminate is decomposed by C0 2 carbonization to obtain Al(OH) 3 , which reacts with the brine to form a stable aluminum lithium compound (LiCl'2Al(OH) 3 'nH 2 0) Precipitation, calcination in the presence of a neutral salt (such as NaN0 3 , NaCl, etc.), which is decomposed into Α1(ΟΗ) 3 and soluble lithium salt, hot water leaching, exchange column of super acid cation exchange resin In addition to impurities, Li + generates LiOH to flow out with the solution; lithium sulfate is added to the NaOH reaction, and impurities such as Fe, Ca, and Mn are removed by filtration, and then frozen to -5 ± 3 ° C, and then Na 2 S (10H 2 O is separated by filtration, and then The filtrate is concentrated by evaporation to crystallize crude LiOH 0, and the crude LiOH 0 is re-dissolved to obtain a LiOH solution, etc., to obtain a LiOH solution having a Li 2 0 concentration of 70±5 g/l, and the impurities are removed to S0 4 2 . The agricultural degree is 8g/l, the concentration of Na 2 0 is 2g/l, and the concentration of CaO is 0.01g/l.
本发明的关键在于 LiOH结晶析出过程中加入微量的不影响 ΟΗ·Η20产品品质 的添加剂、 防板结剂， 调控其析出过程， 使得析出的湿品 ΟΗ·Η20存储过程中不板 结。 避免了干燥后带来的粉尘飞扬问题。 The key point of the present invention is that a small amount of an additive and an anti-caking agent which do not affect the quality of the ΟΗ·Η 20 product are added during the precipitation of LiOH, and the precipitation process is regulated, so that the precipitated wet product 不·Η 20 is not plated during storage. Avoid the problem of dust flying after drying.
为了不引入新的杂质， 在配制溶液和淋洗过程中尽可能使用去离子水。  In order not to introduce new impurities, deionized water is used as much as possible during the formulation and rinsing process.
本发明生产过程简单、 操作容易， 设备投资较少， 产品成本较低， 锂回收率高， 产品质量稳定， 且产品无剌鼻粉尘飞扬， 所生产出的无尘级 ΟΗ·Η20产品完全能够 满足下游行业的品质需要和环保要求。 The invention has the advantages of simple production process, easy operation, less equipment investment, low product cost, high lithium recovery rate, stable product quality, and no flaws in the product, and the dust-free grade ΟΗ·Η 2 0 product completely produced. It can meet the quality needs and environmental requirements of the downstream industry.
具体实施方式 detailed description
实施例 1 电池级无尘 LiOH*H20的制备 Example 1 Preparation of Battery Grade Dust-Free LiOH*H 2 0
( 1 ) 制备 Li20浓度为 70±5g/l的 LiOH溶液 (1) Preparation of a LiOH solution having a Li 2 0 concentration of 70±5 g/l
取 Li20浓度为 38g/L的 Li2S04浸出液 10000ml, 向其加入 Ca(OH;>2调节 pH=7， 过滤， 再向滤液中加入 1080g氢氧化钠， 充分搅拌使其完全溶解，然后在搅拌状况下将其冷至 -3 °C , 当溶液中 S04 2农度在 35g/L时， 将其过滤分离， 得到 LiOH溶液和 Na2S(V 10H2O 固体； 所得到的 LiOH溶液蒸发至液固体积比约为 0.8: 1时， 将其过滤离心分离， 得到 ΟΗ·Η20—次粗品； 加去离子水， 搅拌使其完全溶解， 并使溶液中 Li20浓度为 70g/L， 加入 7.8
Figure imgf000008_0001
, 温度为 45 °C， 搅拌反应 120分钟， 然后将 其过滤分离， 滤液为 LiOH精制纯净液； 其中 Li20浓度为 72g/l的 LiOH溶液， S04 2农度 8g/l， 并控制 Na20浓度 2g/l， CaO浓度 0.01g/l。 Take 10000 ml of Li 2 SO 4 leaching solution with a Li 2 0 concentration of 38 g/L, add Ca (OH; > 2 to adjust pH=7, filter, add 1080 g of sodium hydroxide to the filtrate, and stir well to completely dissolve. Then, it was cooled to -3 °C under stirring, and when the S0 4 2 agronomic degree in the solution was 35 g/L, it was separated by filtration to obtain a LiOH solution and Na 2 S (V 10H 2 O solid; LiOH solution was evaporated to a volume of liquid to solid ratio of about 0.8: 1, filtered centrifuged to obtain ΟΗ · Η 2 0- crude times; deionized water, and stirred to completely dissolve, the solution and the concentration of Li 2 0 At 70g/L, add 7.8
Figure imgf000008_0001
The temperature was 45 ° C, the reaction was stirred for 120 minutes, and then it was separated by filtration. The filtrate was a purified LiOH solution; the Li 2 0 concentration of 72 g/l LiOH solution, S0 4 2 agricultural degree 8g / l, and control Na 2 0 concentration 2g / l, CaO concentration of 0.01g / l.
(2) 结晶制备无尘 LiO&H20 (2) Crystallization preparation of dust-free LiO&H 2 0
将步骤 （1)得到的 LiOH溶液蒸发至液固比为 1:0.9时， 加入防板结剂十二烷基磺 酸钠， 搅拌均匀， 保持料温 901， 离心分离、 洗涤所得固体即为为电池级无尘 When the LiOH solution obtained in the step (1) is evaporated to a liquid-solid ratio of 1:0.9, the anti-caking agent sodium dodecyl sulfate is added, stirred uniformly, and the temperature of the material is maintained at 901. The solid obtained by centrifugation and washing is a battery. Class dust free
ΟΗ·Η20。 真空包装后五个月未出现板结情况。 ΟΗ·Η 2 0. There was no consolidation after five months of vacuum packaging.
实施例 2-24 电池级无尘 LiO&¾0的制备  Example 2-24 Battery Level Dust-free Preparation of LiO&3⁄40
制备过程同实施例 1， 唯不同的是防板结剂的使用量和防板结剂的种类不同。具体 结果见表 1。  The preparation process was the same as in Example 1, except that the amount of the anti-caking agent used and the type of the anti-caking agent were different. The specific results are shown in Table 1.
表 1  Table 1
5天 一个月 三个月 五个月 防板结剂 广口口  5 days, one month, three months, five months, anti-caking agent, wide mouth
实施例 分散剂种类 未出现局 未出现局 未出现局 未出现局 加入比例 合格情况 Example Dispersant Type No Board of Directors No Board of Directors No Board of Directors No Bureaus Added Ratios Qualified
部板结 部板结 部板结 部板结 Knot plate, knot, knot, knot
1 十二烷基磺酸钠 1:1000 合格 V V V V1 sodium dodecyl sulfonate 1:1000 qualified V V V V
2 十二烷基磺酸钠 1:10000 合格 V V V V2 sodium dodecyl sulfate 1:10000 qualified V V V V
3 十二烷基磺酸钠 1:5000 合格 V V V V3 sodium dodecyl sulfonate 1:5000 qualified V V V V
4 亚铁氰化钠 1:800 合格 V V X X4 sodium ferrocyanide 1:800 qualified V V X X
5 亚铁氰化钠 1:500 合格 V V V X5 sodium ferrocyanide 1:500 qualified V V V X
6 亚铁氰化钠 1:1000 合格 V V X X6 sodium ferrocyanide 1:1000 qualified V V X X
7 脂肪酸聚乙二醇酯 1:1000 合格 V X X X7 fatty acid polyethylene glycol ester 1:1000 qualified V X X X
8 脂肪酸聚乙二醇酯 1:800 合格 V X X X8 fatty acid polyethylene glycol ester 1:800 qualified V X X X
9 亚铁氰化钾 1:5000 合格 V V V V9 potassium ferrocyanide 1:5000 qualified V V V V
10 亚铁氰化钾 1:1000 合格 V V V V10 Potassium ferrocyanide 1:1000 Qualified V V V V
11 亚铁氰化钾 1:10000 合格 V V V x + 11 potassium ferrocyanide 1:10000 qualified VVV x +
12 六偏磷酸钠 1:1000 合格 V V X x + 12 Sodium hexametaphosphate 1:1000 Qualified VVX x +
13 六偏磷酸钠 1:800 合格 V V X x + 13 Sodium hexametaphosphate 1:800 Qualified VVX x +
14 六偏磷酸钠 1:500 合格 V V X x + 14 sodium hexametaphosphate 1:500 qualified VVX x +
15 焦磷酸钠 1:1000 合格 V X X x + 15 sodium pyrophosphate 1:1000 qualified VXX x +
16 焦磷酸钠 1:800 合格 V X X x + 16 sodium pyrophosphate 1:800 qualified VXX x +
17 焦磷酸钠 1:500 合格 V X X x + 17 sodium pyrophosphate 1:500 qualified VXX x +
18 硅铝酸钠 1:1000 合格 V X X x + 18 sodium aluminosilicate 1:1000 qualified VXX x +
19 硅铝酸钠 1:500 钠含量超标 V X X x + 19 sodium aluminosilicate 1:500 sodium content exceeds VXX x +
20 磷酸三钙 1:1000 合格 X x + x + x + 20 tricalcium phosphate 1:1000 qualified X x + x + x +
21 磷酸三钙 1:500 钙含量超标 V x + x + x + 21 Tricalcium phosphate 1:500 Calcium content exceeds V x + x + x +
22 三聚磷酸钠 1:800 合格 V X x + x + 22 sodium tripolyphosphate 1:800 qualified VX x + x +
23 三聚磷酸钠 1:500 合格 V X x + x + 23 Sodium tripolyphosphate 1:500 Qualified VX x + x +
24 三聚磷酸钠 1:1000 合格 X x + x + x + 表 1中 表示未出现板结， X表示出现板结， X +表示结块很硬 表 1中的合格是指符合电池级产品标准指标:
Figure imgf000010_0001
从表 1结果可知， 分散剂的选择要注意带入物质对产品杂质含量的影响， 同时部 分分散剂在使用过程中会产生大量的泡沫， 严重影响生产的进行， 分散剂以十二烷基 磺酸钠、 六偏磷酸钠、 亚铁氰化钾、 亚铁氰化钠为好， 不溶性防结剂类化合物易 造成产品杂质含量超标， 不能使用。 24 sodium tripolyphosphate 1:1000 qualified X x + x + x + Table 1 shows that no knots appear, X indicates the occurrence of knots, and X + indicates that the agglomerates are very hard. The pass in Table 1 is in compliance with the standard specifications of battery-level products:
Figure imgf000010_0001
It can be seen from the results in Table 1 that the choice of dispersant should pay attention to the influence of the substance brought into the impurity content of the product, and some dispersants will generate a large amount of foam during use, which seriously affects the production process. The dispersant is dodecyl sulfonate. Sodium, sodium hexametaphosphate, potassium ferrocyanide, sodium ferrocyanide are good, and insoluble anti-caking compounds are likely to cause excessive levels of impurities in the product and cannot be used.
实施例 25-48 工业级无尘 LiO&H20的制备 Example 25-48 Preparation of Industrial Grade Dust-Free LiO&H 2 0
( 1) 制备 Li20浓度为 70±5g/l的 LiOH溶液 (1) Preparation of a LiOH solution having a Li 2 0 concentration of 70±5 g/l
取 Li20浓度为 38g/L的 Li2S04浸出液 10000ml, 向加入 Ca(OH;>2调节 pH=7， 过滤， 再 向滤液中加入 1080g氢氧化钠， 充分搅拌使其完全溶解， 然后在搅拌状况下将其冷至 -3 °C , 当溶液中 S04 2农度在 35g/L时， 将其过滤分离， 得到 LiOH溶液和 Na2S(V10H2O 固体； 所得到的 LiOH溶液蒸发至液固比约为 0.8: 1时， 将其过滤离心分离， 得到Take 10000ml of Li 2 SO 4 leaching solution with Li 2 0 concentration of 38g/L, add Ca (OH; > 2 to adjust pH=7, filter, add 1080g sodium hydroxide to the filtrate, stir well to completely dissolve, then The mixture was cooled to -3 °C under stirring. When the S0 4 2 degree of the solution was 35 g/L, it was separated by filtration to obtain a LiOH solution and Na 2 S (V10H 2 O solid; the obtained LiOH solution) When evaporating to a liquid-solid ratio of about 0.8:1, it is filtered and centrifuged to obtain
ΟΗ·Η20—次粗品； 加去离子水， 搅拌使其完全溶解， 并使溶液中 Li20浓度为 70g/L， 将其过滤分离，滤液为 LiOH纯净液；其中 Li20浓度为 70g/l的 LiOH溶液， S04 2农度 12g/l， 并控制 Na20浓度 5g/l， CaO浓度 0.06g/l。 ΟΗ·Η 2 0—the crude product; adding deionized water, stirring to completely dissolve it, and making the concentration of Li 2 0 in the solution 70g/L, separating and filtering, the filtrate is LiOH pure liquid; wherein the concentration of Li 2 0 is 70 g / l LiOH solution, S0 4 2 agricultural degree 12g / l, and control Na 2 0 concentration 5g / l, CaO concentration 0.06g / l.
(2) 结晶制备无尘 LiO&H20 (2) Crystallization preparation of dust-free LiO&H 2 0
将步骤（1 )得到的 LiOH溶液蒸发至液固比为 1 : 1.2时， 加入防板结剂， 搅拌均匀， 保持料温^90 ， 分离、 洗涤所得固体即为工业级无尘 ΟΗ·Η20。 真空包装后板结情 况见表 2。 表 2 The LiOH solution obtained in the step (1) is evaporated to a liquid-solid ratio of 1:1.2, the anti-caking agent is added, the mixture is evenly stirred, and the temperature of the material is maintained at 90°, and the solid obtained by separation and washing is industrial-grade dust-free ΟΗ·Η 2 0 . The condition of the tube after vacuum packaging is shown in Table 2. Table 2
5天 一个月 三个月 五个月 防板结剂 广口口  5 days, one month, three months, five months, anti-caking agent, wide mouth
实施例 分散剂种类 未出现局 未出现局 未出现局 未出现局 加入比例 合格情况 Example Dispersant Type No Board of Directors No Board of Directors No Board of Directors No Bureaus Added Ratios Qualified
部板结 部板结 部板结 部板结 Knot plate, knot, knot, knot
25 十二烷基磺酸钠 1:1000 合格 V V V V25 sodium dodecyl sulfate 1:1000 qualified V V V V
26 十二烷基磺酸钠 1:10000 合格 V V V V26 sodium dodecyl sulfate 1:10000 qualified V V V V
27 十二烷基磺酸钠 1:5000 合格 V V V V27 sodium dodecyl sulfonate 1:5000 qualified V V V V
28 亚铁氰化钠 1:800 合格 V V X X28 sodium ferrocyanide 1:800 qualified V V X X
29 亚铁氰化钠 1:500 合格 V V V X29 sodium ferrocyanide 1:500 qualified V V V X
30 亚铁氰化钠 1:1000 合格 V V X X30 sodium ferrocyanide 1:1000 qualified V V X X
31 脂肪酸聚乙二醇酯 1:1000 合格 V X X X31 fatty acid polyethylene glycol ester 1:1000 qualified V X X X
32 脂肪酸聚乙二醇酯 1:800 合格 V X X X32 fatty acid polyethylene glycol ester 1:800 qualified V X X X
33 亚铁氰化钾 1:5000 合格 V V V V33 potassium ferrocyanide 1:5000 qualified V V V V
34 亚铁氰化钾 1:1000 合格 V V V V34 Potassium ferrocyanide 1:1000 Qualified V V V V
35 亚铁氰化钾 1:10000 合格 V V V x + 35 potassium ferrocyanide 1:10000 qualified VVV x +
36 六偏磷酸钠 1:1000 合格 V V X x + 36 Sodium hexametaphosphate 1:1000 Qualified VVX x +
37 六偏磷酸钠 1:800 合格 V V X x + 37 Sodium hexametaphosphate 1:800 Qualified VVX x +
38 六偏磷酸钠 1:500 合格 V V X x + 38 Sodium hexametaphosphate 1:500 Qualified VVX x +
39 焦磷酸钠 1:1000 合格 V X X x + 39 sodium pyrophosphate 1:1000 qualified VXX x +
40 焦磷酸钠 1:800 合格 V X X x + 40 sodium pyrophosphate 1:800 qualified VXX x +
41 焦磷酸钠 1:500 合格 V X X x + 41 sodium pyrophosphate 1:500 qualified VXX x +
42 硅铝酸钠 1:1000 合格 V X X x + 42 sodium aluminosilicate 1:1000 qualified VXX x +
43 硅铝酸钠 1:500 合格 V X x + x + 43 sodium aluminosilicate 1:500 qualified VX x + x +
44 磷酸三钙 1:1000 合格 V X x + x + 44 Tricalcium Phosphate 1:1000 Qualified VX x + x +
45 磷酸三钙 1:500 合格 V X x + x + 45 tricalcium phosphate 1:500 qualified VX x + x +
46 三聚磷酸钠 1:800 合格 V X x + x + 46 Sodium tripolyphosphate 1:800 Qualified VX x + x +
47 三聚磷酸钠 1:500 合格 V X x + x + 47 Sodium tripolyphosphate 1:500 Qualified VX x + x +
48 三聚磷酸钠 1:1000 合格 V X x + x + 48 Sodium tripolyphosphate 1:1000 Qualified VX x + x +

Claims

权利要求书 Claim
1、 单水氢氧化锂， 其特征在于： 所述单水氢氧化锂为疏松的颗粒状湿品， 其中， 水份含量 3.5%， 单水氢氧化锂表面包裹微量的防板结剂， 所述防板结剂为十二烷基 磺酸钠、 亚铁氰化钠、 亚铁氰化钾、 六偏磷酸钠、 三聚磷酸钠、 焦磷酸钠、 十二 醇硫酸钠、 聚丙烯酰胺、 甲基戊醇、 三乙基己基磷酸或纤维素衍生物中的一种； 其中， 防板结剂的重量为 l〜10ppm。  1. Lithium hydroxide monohydrate, characterized in that: the lithium hydroxide monohydrate is a loose granular wet product, wherein the moisture content is 3.5%, and the surface of the lithium hydroxide monohydrate is coated with a trace amount of anti-caking agent, The anti-caking agent is sodium dodecyl sulfate, sodium ferrocyanide, potassium ferrocyanide, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium decol sulfate, polyacrylamide, methyl One of pentanol, triethylhexylphosphoric acid or a cellulose derivative; wherein the weight of the anti-caking agent is from 1 to 10 ppm.
2、根据权利要求 1所述的单水氢氧化锂， 其特征在于： 所述防板结剂为十二烷基 磺酸钠、 六偏磷酸钠、 亚铁氰化钾或亚铁氰化钠中的一种。  The lithium hydroxide monohydrate according to claim 1, wherein the anti-caking agent is sodium dodecyl sulfate, sodium hexametaphosphate, potassium ferrocyanide or sodium ferrocyanide. One kind.
3、根据权利要求 1或 2所述的单水氢氧化锂， 其特征在于： 它是由以下方法制备 而成：  The lithium hydroxide monohydrate according to claim 1 or 2, which is prepared by the following method:
( 1 ) 制得 Li20浓度为 70±5g/l的 LiOH溶液， 其中， 控制 S04 2农度 15g/l; (1) obtaining a LiOH solution having a Li 2 0 concentration of 70±5 g/l, wherein, the S0 4 2 agricultural degree is controlled by 15 g/l;
(2) 将步骤 （1 ) 得到的 LiOH溶液蒸发至液固比为 1 :0.8〜1.5时加入微量防板 结剂， 搅拌均匀， 分离、 洗涤即得无尘、 不板结的工业级 ΟΗ·Η20产品； (2) Evaporate the LiOH solution obtained in step (1) until the liquid-solid ratio is 1:0.8~1.5, add a small amount of anti-caking agent, stir evenly, separate and wash to obtain dust-free, non-knotted industrial grade ΟΗ·Η 2 0 product;
其中， 所述防板结剂加入时， LiOH溶液的温度保持 90〜100°C， 防板结剂的加入 量为： 防板结剂的重量与物料中 LiOH的重量比 =1 : 1000〜10000。  Wherein, when the anti-caking agent is added, the temperature of the LiOH solution is maintained at 90 to 100 ° C, and the amount of the anti-caking agent is: the weight ratio of the anti-caking agent to the LiOH in the material = 1 : 1000 to 10000.
4、 根据权利要求 3所述的单水氢氧化锂， 其特征在于： 步骤（1 )控制 S04 2农度 8g/l， 并控制 Na20浓度 2g/l， CaO浓度 0.01g/l。 4. The lithium hydroxide monohydrate according to claim 3, wherein: step (1) controls S0 4 2 agricultural degree 8 g/l, and controls a Na 2 0 concentration of 2 g/l, and a CaO concentration of 0.01 g/l.
5、 根据权利要求 3所述的单水氢氧化锂， 其特征在于： 步骤 （2) 加入分散剂时 LiOH溶液蒸发至液固体积比为 1 :0.8〜1.1。  The lithium hydroxide monohydrate according to claim 3, wherein: (2) the LiOH solution is evaporated to a liquid solid ratio of 1:0.8 to 1.1 when the dispersant is added.
6、 单水氢氧化锂的制备方法， 其特征在于： 它是由以下步骤完成：  6. A method for preparing lithium hydroxide monohydrate, characterized in that: it is completed by the following steps:
( 1 ) 制得 Li20浓度为 70±5g/l的 LiOH溶液， 其中， 控制 S04 2农度 15g/l; (1) obtaining a LiOH solution having a Li 2 0 concentration of 70±5 g/l, wherein, the S0 4 2 agricultural degree is controlled by 15 g/l;
(2) 将步骤 （1 ) 得到的 LiOH溶液蒸发至液固比为 1 :0.8〜1.5时加入微量防板 结剂， 搅拌均匀， 分离、 洗涤即得无尘工业级 ΟΗ·Η20产品， 真空密封包装即得； 其中， 所述防板结剂加入时， LiOH溶液的温度保持 90〜100°C， 所述防板结剂为 十二烷基磺酸钠、 亚铁氰化钠、 亚铁氰化钾、 六偏磷酸钠、 三聚磷酸钠、 焦磷酸 钠、 十二醇硫酸钠、 聚丙烯酰胺、 甲基戊醇、 三乙基己基磷酸或纤维素衍生物中 的一种； 防板结剂的加入量为： 防板结剂的重量与物料中 LiOH 的重量比 =1 : 1000〜 10000。 (2) Evaporate the LiOH solution obtained in step (1) until the liquid-solid ratio is 1:0.8~1.5, add a small amount of anti-caking agent, stir evenly, separate and wash to obtain dust-free industrial grade ΟΗ·Η 2 0 product, vacuum The sealed package is obtained; wherein, when the anti-caking agent is added, the temperature of the LiOH solution is maintained at 90 to 100 ° C, and the anti-caking agent is sodium dodecyl sulfate, sodium ferrocyanide, ferrocyanide One of potassium, sodium hexametaphosphate, sodium tripolyphosphate, sodium pyrophosphate, sodium decol sulfate, polyacrylamide, methylpentanol, triethylhexylphosphoric acid or a cellulose derivative; The amount added is: the weight ratio of the anti-caking agent to the weight of LiOH in the material = 1: 1000~ 10000.
7、 根据权利要求 6所述的单水氢氧化锂的制备方法， 其特征在于： 步骤 （1 ) 控 制 S04 2-浓度 8g/l， 并控制 Na20浓度 2g/l， CaO浓度 0.01g/l。 7. The method for preparing lithium hydroxide monohydrate according to claim 6, wherein: step (1) is controlled S0 4 2 - concentration 8g / l, and control Na 2 0 concentration 2g / l, CaO concentration 0.01g / l.
8、 根据权利要求 6所述的单水氢氧化锂的制备方法， 其特征在于： 步骤 （2) 加 入分散剂时 LiOH溶液蒸发至液固体积比为 1:0.8〜1.1。 The method for producing lithium hydroxide monohydrate according to claim 6, wherein: (2) the LiOH solution is evaporated to a liquid solid ratio of 1:0.8 to 1.1 when the dispersant is added.
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