Composite additive for treating lepidolite ore and application thereof
阅读说明：本技术 一种处理锂云母矿的复合添加剂及其应用 (Composite additive for treating lepidolite ore and application thereof ) 是由 杨成浩 熊训辉 钟文涛 于 2020-04-21 设计创作，主要内容包括：本发明公开了一种处理锂云母矿的复合添加剂及其应用,该应用包括以下步骤：将锂云母进行焙烧脱氟,以便得到脱氟焙烧料；将脱氟焙烧料与硫酸富盐、钙盐及复合添加剂进行配料烧结,以便得到焙烧熟料；将焙烧熟料进行破碎浸出,以得到集锂、铷、铯的浸出液。本发明利用在高温烧结过程中,复合添加剂与锂云母中的铝、硅等元素形成难溶复盐,实现与锂、铷、铯的有效分离,在随后的浸出中,能将85%以上的锂及70%的铷、铯浸出。本发明提出的复合添加剂成本低廉,简单易行,能有效实现矿相转型,提高有价元素的浸出率,同时,大大降低硫酸盐法中硫酸钠、硫酸钾等硫酸盐的使用量,降低硫酸盐法处理锂云母矿的生产成本。(The invention discloses a composite additive for treating lepidolite ore and application thereof, wherein the application comprises the following steps: roasting and defluorinating lepidolite to obtain defluorinated roasted material; mixing and sintering the defluorinated roasting material, rich sulfate salt, calcium salt and composite additive to obtain roasted clinker; and crushing and leaching the roasted clinker to obtain a leaching solution for collecting lithium, rubidium and cesium. The invention realizes effective separation from lithium, rubidium and cesium by using the indissolvable double salt formed by the composite additive and elements such as aluminum, silicon and the like in lepidolite in the high-temperature sintering process, and can leach more than 85 percent of lithium and 70 percent of rubidium and cesium in subsequent leaching. The composite additive provided by the invention is low in cost, simple and feasible, can effectively realize ore phase transformation, improves the leaching rate of valuable elements, greatly reduces the usage amount of sulfate such as sodium sulfate, potassium sulfate and the like in a sulfate method, and reduces the production cost of treating lepidolite ore by the sulfate method.)
1. The composite additive for treating lepidolite ore is characterized by being added in a sintering process after lepidolite roasting and defluorination, and comprises one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sulfide, potassium carbonate, potassium bicarbonate, potassium hydroxide, potassium chloride, aluminum potassium sulfate, magnesium oxide, magnesium chloride, magnesium sulfate, magnesium carbonate, manganese sulfate, manganese carbonate, ferric sulfate, ferrous sulfate, barium titanate, calcium titanate, barium sulfate, strontium carbonate, strontium chloride, strontium oxide, cerium carbonate, chromium sulfate, chromium chloride, yttrium oxide and composite rare earth.
2. The additive package for treating lepidolite ore according to claim 1 wherein the additive package is one of magnesium oxide in combination with strontium carbonate, barium sulfate in combination with manganese sulfate, magnesium chloride in combination with chromium sulfate, potassium chloride in combination with chromium sulfate, magnesium chloride in combination with chromium sulfate and manganese sulfate.
3. The use of the composite additive for treating lepidolite ore according to claim 1 or 2, comprising the steps of:
1) roasting and defluorination: introducing steam to perform defluorination roasting on the lepidolite ore to obtain the defluorinated lepidolite ore;
2) burdening and sintering: mixing the defluorinated lepidolite ore obtained in the step 1) with a compound of sulfate and calcium and a composite additive according to the proportion of 1: 0.1-0.6: 0.05-0.3: adding water in a mass ratio of 0.01-0.2, wet grinding, drying, sintering and cooling to obtain a lepidolite sintering material;
3) crushing and leaching: leaching the lepidolite sintering material obtained in the step 2), and performing solid-liquid separation to obtain a leaching solution rich in Li, Rb and Cs.
4. The use according to claim 3, wherein the lepidolite ore of step 1) has a size of 100 to 325 mesh; the temperature of the defluorination roasting is 500-950 ℃, and the time of the defluorination roasting is 10-60 min; the introduction amount of the water vapor is 0.005m per ton of lepidolite ore3/h ~ 0.03 m3/h。
5. The use of claim 3, wherein the sulfate salt of step 2) is one or more of sodium sulfate and potassium sulfate.
6. The use according to claim 3, wherein the calcium compound in step 2) is one or more of calcium oxalate, calcium sulfate, calcium oxide, calcium carbonate, calcium chloride and calcium formate.
7. The use according to claim 3, wherein the wet milling in step 2) is carried out for a period of 2 to 8 hours.
8. The use of claim 3, wherein the sintering temperature in step 2) is 700-1050 ℃ and the sintering time is 0.2-6 h.
9. The use according to claim 3, wherein the leaching agent used in the leaching process of step 3) is water; the liquid-solid mass ratio of the water to the lepidolite sintering material is 1-3: 1.
10. the application of claim 3, wherein in the step 3), before leaching, the lepidolite sintering material obtained in the step 2) is crushed and ground to 100-325 meshes; the leaching temperature is 20-80 ℃, and the leaching time is 0.5-5 h.
Technical Field
The invention relates to the field of lepidolite sintering additives, in particular to a composite additive for treating lepidolite ore and application thereof.
Background
The extraction method of lithium resources is mainly divided into two types: extracting lithium from salt lake brine and extracting lithium from minerals. The salt lake lithium resource reserves are abundant, the lithium extraction process is mature, and the cost is low, so that the method mainly extracts lithium from brine internationally. However, the lithium content in brine in China is low, the magnesium and lithium content is high, the extraction difficulty is high, and the implementation difficulty of the industrial brine lithium extraction technology in China is high. Extracting lithium from the ore, namely performing pyrogenic roasting or wet leaching treatment on the lithium-containing mineral to destroy the mineral structure, releasing valuable alkali metal elements such as Li, Rb, Cs and the like in the lithium-containing mineral in a soluble salt mode, and purifying and enriching to extract valuable lithium salts such as lithium carbonate, lithium hydroxide and the like and valuable Rb and Cs byproducts. The main lithium-containing mineral resources for extracting lithium from the ore are spodumene and lepidolite, wherein the spodumene extraction has the advantages of simple process, mature process, high production efficiency, low energy consumption, high lithium recovery rate and the like, and is the main lithium source for extracting lithium from minerals in China. However, in China, the reserve of spodumene is small, the ore deposit is small in scale and distributed dispersedly, and the sources of the spodumene used in industry mainly depend on import from abroad. In lepidolite ore, the mineral is rich in multiple valuable elements with high added values, such as lithium, rubidium, cesium and the like, is an important resource for extracting rubidium and cesium, is rich in reserves and concentrated in distribution in China, and is a lithium resource mineral with great development value.
Compared with the extraction of lithium from spodumene, the production process of extracting lithium from lepidolite is complex, the production cost is high, the technology is laggard, and further research and development are needed. The currently used and researched methods for extracting lithium from lepidolite in domestic and foreign industries mainly comprise a limestone roasting method, a sulfate roasting method, a sulfation roasting method, a chlorination roasting method, an alkali pressure cooking method and the like. The sulfate roasting method is widely applied to extracting lithium from lepidolite, but the traditional sulfate roasting process has the disadvantages of large consumption of potassium sulfate and sodium sulfate, high production cost, strict requirement on sintering temperature and difficult guarantee of lithium yield.
Disclosure of Invention
The invention aims to provide the compound additive for treating lepidolite ore by the sulfate roasting method with simple components and the application thereof, which can effectively destroy the vein structure, reduce the consumption of sulfate in the sulfate roasting process, reduce the production cost and improve the leaching rate of valuable elements such as lithium, rubidium, cesium and the like.
The purpose of the invention is realized by the following technical scheme.
A composite additive for treating lepidolite ore by a sulfate roasting method is added in a sintering process after lepidolite roasting defluorination, and comprises one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium sulfide, potassium carbonate, potassium bicarbonate, potassium hydroxide, potassium chloride, aluminum potassium sulfate, magnesium oxide, magnesium chloride, magnesium sulfate, magnesium carbonate, manganese sulfate, manganese carbonate, ferric sulfate, ferrous sulfate, barium titanate, calcium titanate, barium sulfate, strontium carbonate, strontium chloride, strontium oxide, cerium carbonate, chromium sulfate, chromium chloride, yttrium oxide and composite rare earth.
The reaction principle is as follows:
MeAl(Si4O10)OH2+CaX→3CaO·Al2O3·3SiO2+MeX
MeAl(Si4O10)OH2+(Na,K)X→(Na,K)2O·Al2O3·2SiO2+MeX
MeAl(Si4O10)OH2+MgX→Al2Mg(SiO4)2+MeX
MeAl(Si4O10)OH2+(Fe,Mn)X→(Fe,Mn)3Al2(SiO4)3+MeX
MeAl(Si4O10)OH2+(Cr,V,Ti)X→Ca3(Cr,V,Zr,Ti)2(SiO4)3+MeX
MeAl(Si4O10)OH2+YX→Y3Al2(AlO4)3+MeX
wherein Me represents Li, Rb, Cs, Na, K and other alkali metal elements, and X represents SO4 2-、O2-、Cl-、CO3 2-、OH-And the like form soluble salt anions with alkali metals.
Preferably, the composite additive is one of a combination of magnesium oxide and strontium carbonate, a combination of barium sulfate and manganese sulfate, a combination of magnesium chloride and chromium sulfate, a combination of potassium chloride and chromium sulfate, and a combination of magnesium chloride, chromium sulfate and manganese sulfate.
The application of the composite additive for treating lepidolite ore by the sulfate roasting method comprises the following steps:
1) roasting and defluorination: introducing steam to perform defluorination roasting on the lepidolite ore to obtain the defluorinated lepidolite ore;
2) burdening and sintering: mixing the defluorinated lepidolite ore obtained in the step 1) with a compound of sulfate and calcium and a composite additive according to the proportion of 1: 0.1-0.6: 0.05-0.3: adding water in a mass ratio of 0.01-0.2, wet grinding, drying, sintering and cooling to obtain a lepidolite sintering material;
3) crushing and leaching: leaching the lepidolite sintering material obtained in the step 2), and performing solid-liquid separation to obtain a leaching solution rich in Li, Rb and Cs.
Preferably, the size of the lepidolite ore in the step 1) is 100-325 meshes; the temperature of the defluorination roasting is 500-950 ℃, and the time of the defluorination roasting is 10-60 min; the introduction amount of the water vapor is 0.005m per ton of lepidolite ore3/h～0.03m3H is used as the reference value. The purpose of step 1) of the invention is to separate lithium from fluorine, reduce the stability of lepidolite, and the reaction principle is as follows:
KLiAl(Si4O10)(F,OH)+H2O→HF+KLiAl(Si4O10)OH2。
preferably, the sulfate in step 2) is one or more of sodium sulfate and potassium sulfate.
Preferably, the calcium compound in step 2) is one or more of calcium oxalate, calcium sulfate, calcium oxide, calcium carbonate, calcium chloride and calcium formate.
Preferably, the time for wet grinding in the step 2) is 2-8 h.
Preferably, the sintering temperature in the step 2) is 700-1050 ℃, and the sintering time is 0.2-6 h.
The purpose of step 2) of the invention is to realize effective separation of lithium, rubidium and cesium from aluminum and silicon.
Preferably, the leaching reagent used in the leaching process in the step 3) is water; the liquid-solid mass ratio of the water to the lepidolite sintering material is 1-3: 1.
preferably, in the step 3), before leaching, the lepidolite sintering material obtained in the step 2) is crushed and ground to 100-325 meshes; the leaching temperature is 20-80 ℃, and the leaching time is 0.5-5 h.
The step 3) of the invention aims to separate lithium, rubidium and cesium from impurity phases, and the reaction principle is as follows:
MeX+H2O→MeOH+HX。
the composite additive of the invention includes, but is not limited to, the sulfate roasting lepidolite process, and is also suitable for other high-temperature roasting treatment processes of lepidolite ore.
Compared with the prior art, the invention has the following advantages:
the composite additive is simple and easy to implement, has low cost, can effectively destroy the bonding strength of alkali metals such as Li, Rb, Cs and the like and impurities such as Al, Si and the like by using a small amount of additive, releases free Li, Rb, Cs, reduces the dissolving difficulty of Li, Rb, Cs in the subsequent leaching process, effectively improves the leaching rate of Li, Rb, Cs, and has wide market prospect and better economic and social benefits.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
The lepidolite mineral is used as a raw material, and the main chemical components are shown in the following table 1:
TABLE 1
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