CN101885496B - Process for extracting lithium from lithionite by fluorine chemistry - Google Patents

Process for extracting lithium from lithionite by fluorine chemistry Download PDF

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Publication number
CN101885496B
CN101885496B CN2010102351502A CN201010235150A CN101885496B CN 101885496 B CN101885496 B CN 101885496B CN 2010102351502 A CN2010102351502 A CN 2010102351502A CN 201010235150 A CN201010235150 A CN 201010235150A CN 101885496 B CN101885496 B CN 101885496B
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lithionite
reaction
reactor
lithium
additive
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CN101885496A (en
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旷戈
林诚
王占前
叶长燊
林荣英
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Jiangxi Hai Hui Long Zhou Lithium Industry Co., Ltd.
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Fuzhou University
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Abstract

The invention provides a process for extracting lithium from lithionite by fluorine chemistry, comprising the following steps: throwing raw materials of lithionite powder, an additive and sulfuric acid based on the weight ratio of 1: (0.1-2): (0.5-5) into a pre-reactor, and then stirring to react or simply stirring and then throwing the raw materials into the reactor to react, wherein, the additive is one or more of a fluorine-containing mineral substance, salt or acid; reaction conditions in the pre-reactor are as follows: preheating the raw materials at the temperature of 50-150 DEG C for 0.1-2 hours, and then transferring into the reactor to react at the temperature of 150-350 DEG C for 0.5-4 hours; immediately evacuating the gas generated during the reaction process; leaching the obtained reaction residue with water and then carrying out liquid-solid separation to obtain a sulfate liquor; and adjusting pH into 5.0-10.0 to eliminate ionic impurities such as aluminum, magnesium, calcium, ferrum and the like; and after the liquid-solid separation is carried out, concentrating the sulfate liquor, precipitating lithium ions and then filtering to obtain a crude lithium salt product or the corresponding refined lithium salt product as required. The process of the invention has the advantages of low reaction temperature, small production energy consumption and high lithium extraction efficiency; and various valuable components of the lithionite mineral substance can be comprehensively utilized during the production process of lithium salt.

Description

Process for extracting lithium from lithionite by fluorine chemistry
Technical field
The present invention relates to a kind of ore and put forward the lithium technical field, more specifically is a kind of process for extracting lithium from lithionite by fluorine chemistry.
Background technology
Lithium and lithium salts expand to high-technology fields such as Al-Li alloy, lithium cell, nucleosynthesis by traditional Application Areas such as glass-ceramic, electrolytic aluminum, lubricating grease, refrigeration etc., the particularly new forms of energy explosive type demand growth that may exist for efficient store battery, technical progress to lithium salts industry has proposed urgent challenge, studies new lithium minerals and puies forward the lithium technology development of world's new forms of energy is had crucial meaning.
The main raw material of carrying lithium at present is salt lake brine and solid lithium minerals, and the reserves of Chinese lithionite and triphane are abundant.The method of carrying lithium from lithium minerals mainly contains sulphate process, chloride process, limestone-based process, sulfuric acid process and gas-solid reaction method.These methods all are that lithium minerals is carried out high-temperature calcination, handle the calcining slag with diverse ways then and further produce lithium salts, exist the production cost height, energy consumption is big, the lithium extraction yield is low, and the waste residue amount is big, and industrial significance is produced outstanding problems such as only can utilizing the higher-grade triphane.
Summary of the invention
The present invention is directed to above problem, proposed a kind of process for extracting lithium from lithionite by fluorine chemistry.The present invention has proposed to utilize the character of the distinctive destruction silicate minerals of fluorine chemistry crystalline structure first, adopt lithionite for carrying the lithium raw material, under relatively low temperature of reaction temperature, just can destroy the layered crystal structure of lithionite densification, reach the purpose of efficiently carrying lithium, greatly reduce the energy consumption in the production process, when producing lithium salts, also can fully utilize the various valuable components of lithionite mineral.
Technical program of the present invention lies in: a kind of process for extracting lithium from lithionite by fluorine chemistry is characterized in that: click step and carry out:
1) raw material mica powder, additive, sulfuric acid are put into preheating and evenly stirring in the pre-reactor;
2) preheating and the material that stirs are transferred to finish reaction in the reactor or finish reaction in the reactor without entering after preheating directly mixes, the gas that produces in the reaction process is in time extracted out;
3) reaction slag with water extraction after, liquid-solid separation obtains sulfate liquor, the pH that regulates this solution is to remove aluminium, magnesium, calcium, iron plasma impurity;
4) with after the impurity elimination, solution concentrates, and precipitation lithium ion after-filtration gets thick lithium salts product, as required, produces corresponding refined lithium salt.
The invention has the advantages that.
1, operational path provided by the present invention does not need high-temperature calcination, utilizes the characteristic of fluorine chemistry corrosion Si oxide, and the employing additive than destroying the lithium minerals crystalline structure under the low reaction temperatures, has been saved production energy consumption with sulfuric acid greatly.
2, the fluorine in the reaction mass of the present invention separates with the reaction slag with the form of silicon fluoride, hydrogen fluoride gas, and be absorbed and obtain silicofluoric acid or silicofluoride is used for producing the fluoride salt product, the reaction slag is gone out the sulfate liquor that the back obtains to contain lithium by water logging, filter residue is mainly calcium sulfate, can be used as the crown filler and is used.
3, the sulfate liquor that contains lithium of the present invention's acquisition is behind impurity such as precipitation of aluminium, iron, magnesium, calcium, and further precipitate and separate obtains lithium salts, the solution of post precipitation, but condensing crystal obtains potassium, sodium salt.
4, technology of the present invention has lithium extraction yield height, and can fully utilize various valuable compositions realization coproduction in the mineral, and comprehensive benefit is good, and production cost is low, production energy consumption is little, advantages such as non-environmental-pollution hidden danger.
Embodiment
A kind of process for extracting lithium from lithionite by fluorine chemistry is characterized in that: click step and carry out:
1) raw material mica powder, additive, sulfuric acid are put into preheating and evenly stirring in the pre-reactor;
2) preheating and the material that stirs are transferred to finish reaction in the reactor or finish reaction in the reactor without entering after preheating directly mixes, the gas that produces in the reaction process is in time extracted out;
3) reaction slag with water extraction after, liquid-solid separation obtains sulfate liquor, the pH that regulates this solution is to remove aluminium, magnesium, calcium, iron plasma impurity;
4) with after the impurity elimination, solution concentrates, and precipitation lithium ion after-filtration gets thick lithium salts product, as required, produces corresponding refined lithium salt.
The feed product weight ratio is a lithionite: additive: sulfuric acid=1:(0.1-2): (0.5-5).
Described additive is one or more of fluorine-containing mineral, salt or acid.
Li in the lithionite powder in the feed product 2The content of O 〉=3.0%, the content of F 〉=10% in the additive, H in the sulfuric acid 2SO 4Content 〉=50%.
Preheating temperature in pre-reactor is 50-150 ℃, and be 0.1-2 hour warm up time.
Material enters in the reactor, is 150-350 ℃ in temperature of reaction and reacts 0.5-4 hour down.
The gaseous constituent that produces in the reaction process is mainly silicon tetrafluoride, water vapour, hydrogen fluoride, absorbs by water or alkaline solution after the cooling dedusting.
Regulating pH is 5.0-10.0 with the pH scope of removing aluminium, magnesium, calcium, iron plasma impurity.
Embodiment 1: the feed product weight ratio is a lithionite: additive: sulfuric acid=1:0.1:0.5, described additive is 30% hydrofluoric acid, pre-reaction temperature in the pre-reactor is 50 ℃, be 0.1 hour warm up time, mixture enters in the reactor, being 150-350 ℃ in temperature of reaction reacted 4 hours down, reaction process progressively heats up, temperature reaches 350 ℃ of afterreactions and finishes, the reaction slag with water extraction after, liquid-solid separation obtains sulfate liquor, and the pH that regulates this solution is to remove aluminium, magnesium, calcium, iron plasma impurity; After the impurity elimination, solution concentrates, and precipitation lithium ion after-filtration gets thick lithium salts product more than 80%, according to the purposes needs, produces corresponding refined lithium salt.
Embodiment 2: the feed product weight ratio is a lithionite: additive: sulfuric acid=1:2:5, described additive are 70% Calcium Fluoride (Fluorspan).Pre-reaction temperature in the pre-reactor is 150 ℃, be 1 hour warm up time, mixture enters in the reactor, being 150-350 ℃ in temperature of reaction reacted 4 hours down, reaction process progressively heats up, and temperature reaches 350 ℃ of afterreactions and finishes, the reaction slag with water extraction after, liquid-solid separation obtains sulfate liquor, and the pH that regulates this solution is to remove aluminium, magnesium, calcium, iron plasma impurity; After the impurity elimination, solution concentrates, and precipitation lithium ion after-filtration gets thick lithium salts product more than 80%, according to the purposes needs, produces corresponding refined lithium salt.
Embodiment 3: the feed product weight ratio is a lithionite: additive: sulfuric acid=1:1:3, described additive is 70% Calcium Fluoride (Fluorspan) and the mixing of 30% hydrofluoric acid, pre-reaction temperature in the pre-reactor is 150 ℃, be 1 hour warm up time, mixture enters in the reactor, being 150-350 ℃ in temperature of reaction reacted 4 hours down, reaction process progressively heats up, temperature reaches 350 ℃ of afterreactions and finishes, the reaction slag with water extraction after, liquid-solid separation obtains sulfate liquor, and the pH that regulates this solution is to remove aluminium, magnesium, calcium, iron plasma impurity; After the impurity elimination, solution concentrates, and precipitation lithium ion after-filtration gets thick lithium salts product more than 80%, according to the purposes needs, produces corresponding refined lithium salt.

Claims (3)

1. process for extracting lithium from lithionite by fluorine chemistry is characterized in that: carry out by the following step:
1) raw material lithionite, additive, sulfuric acid are put into preheating and reaction in the pre-reactor, evenly stirred;
2) material that stirs behind preheating and the initial reaction is transferred to finishes reaction in the reactor or finish reaction in the reactor without entering after preheating directly mixes, the gas that produces in the reaction process is in time extracted out;
3) reaction slag with water extraction after, liquid-solid separation obtains sulfate liquor, the pH that regulates this solution is to remove aluminium, magnesium, calcium, iron ion impurity;
4) with after the impurity elimination, solution concentrates, and precipitation lithium ion after-filtration gets thick lithium salts product, as required, produces corresponding refined lithium salt;
The feed product weight ratio is a lithionite: additive: sulfuric acid=1:(0.1-2): (0.5-5);
Described additive is one or more of fluorine-containing mineral, salt or acid;
Li in the lithionite powder in the feed product 2The content of O 〉=3.0%, the content of F 〉=10% in the additive, H in the sulfuric acid 2SO 4Content 〉=50%;
Preheating temperature in pre-reactor is 50-150 ℃, and be 0.1-2 hour warm up time;
Material enters in the reactor, is 150-350 ℃ in temperature of reaction and reacts 0.5-4 hour down.
2. process for extracting lithium from lithionite by fluorine chemistry according to claim 1 is characterized in that: the gaseous constituent that produces in the reaction process is mainly silicon tetrafluoride, water vapour and hydrogen fluoride, absorbs by water or alkaline solution after the cooling dedusting.
3. process for extracting lithium from lithionite by fluorine chemistry according to claim 1 is characterized in that: regulating pH is 5.0-10.0 with the pH scope of removing aluminium, magnesium, calcium, iron ion impurity.
CN2010102351502A 2010-07-23 2010-07-23 Process for extracting lithium from lithionite by fluorine chemistry Active CN101885496B (en)

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CN102586587B (en) * 2012-03-24 2013-10-23 宜春合纵锂业科技有限公司 Method for treating lepidolite ore
CN102649996A (en) * 2012-05-24 2012-08-29 张韵 Circular acid leaching extraction process for lepidolite
CN103145158B (en) * 2013-02-28 2014-11-05 江西赣锋锂业股份有限公司 Method for preparing lithium carbonate from lepidolite through sulfuric acid roasting method
CN106319245B (en) * 2016-09-19 2018-05-04 福州大学 A kind of method that lepidolite successive reaction carries lithium
CN106673021A (en) * 2016-12-23 2017-05-17 江西合纵锂业科技有限公司 Method for circularly extracting lithium from lithium mica as raw material
CN108910851B (en) * 2018-09-21 2021-12-31 深圳市德方纳米科技股份有限公司 Method for preparing lithium-containing compound from lithium-phosphorus-aluminum

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JPS5948870B2 (en) * 1977-09-13 1984-11-29 Asahi Glass Co Ltd
CN1003008B (en) * 1985-04-01 1989-01-04 广州有色金属研究院 Technology for preparation of li2co3 by treating lithium-loaded mica with k2so4
CN1827527A (en) * 2005-03-02 2006-09-06 钟辉 Process for preparing lithium chlorate by lithium extracted from lepidolite
CN100503849C (en) * 2006-11-24 2009-06-24 江西赣锋锂业股份有限公司 Method for producing refined lithium sulfate solution used in lepidolite lithium-extracting technique by sulfuric acid process

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