CN102295303A

CN102295303A - Extraction method of lithium carbonate

Info

Publication number: CN102295303A
Application number: CN2011102254456A
Authority: CN
Inventors: 张勇
Original assignee: JIANGSU ORIGIN SCIENCE AND TECHNOLOGY NEW MATERIALS Co Ltd
Current assignee: JIANGSU ORIGIN SCIENCE AND TECHNOLOGY NEW MATERIALS Co Ltd
Priority date: 2011-08-08
Filing date: 2011-08-08
Publication date: 2011-12-28
Anticipated expiration: 2031-08-08
Also published as: CN102295303B

Abstract

The invention discloses an extraction method of lithium carbonate. With lithionite being used as a raw material, the extraction method comprises the following steps of: 1) calcining to remove fluorine: placing a lepidolite powder into a tilting furnace for calcining, followed by crushing; 2) acid leaching: carrying out an impregnation reaction on the crushed lithionite by the use of a sulphuric acid solution; 3) filtering and removing residues: filtering the above solid-liquid mixed solution and removing filter residues to obtain a mother liquor 1; 4) freezing and separating: adding an aluminium hydroxide solution into the mother liquor 1, freezing, separating out potassium, aluminium, rubidium and cesium alum to obtain a mother liquor 2; 5) depositing lithium and separating to prepare the product: adding liquefied ammonia into the mother liquor 2, filtering and separating to remove residues, adding a calcium hydrate emulsion into the filtrate, followed by neutralization and condensation, adding a sodium carbonate solution into a concentrate for a reaction, followed by filtering, separating and solid drying to obtain the lithium carbonate product, wherein the separated filtrate is recovered and reused. By calcining and acid leaching to remove fluorine, the method provided by the invention has advantages of mild condition of the low-temperature extraction technology and low production cost.

Description

Extract the method for Quilonum Retard

Technical field: the present invention relates to a kind of method of extracting Quilonum Retard, particularly from the lithionite raw material, extract the method for Quilonum Retard.

Background technology:Quilonum Retard is a kind of important chemical material, and along with national new forms of energy development program, lithium electricity new forms of energy are as one of state key support development energy industry; And Quilonum Retard develops the important foundation raw material as lithium electricity new forms of energy, and its production and demand are increasing, and price is also more and more higher.

Tantalum niobium lithium ore deposit, Yichuan is the tantalum niobium lithium ore deposit of present Asia maximum, tantalum niobium lithium resource is abundant, the titanium dioxide lithium content reaches 4.5% in the lithionite, has the Quilonum Retard of extraction resources advantage condition, and contain multiple metal values elements such as potassium, rubidium, caesium, aluminium in the lithionite, fully utilize these resources, can significantly improve the utility value of from lithionite, extracting Quilonum Retard, thereby significantly reduce the Quilonum Retard production cost.Therefore be that raw material extracts Quilonum Retard and has than vast market prospect with the lithionite, and favorable economic benefit.

The preparation method of Quilonum Retard mainly contains solid ore deposit and liquid ore deposit from raw material at present, the liquid ore deposit mainly is to be that raw material extracts with the salt lake brine, this method is because raw materials cost is low, be easy to extract, technology is very ripe, but because magnesium ion content is higher in the bittern, its manufacture level lithium carbonate is easier to, if but its production cost of the Quilonum Retard of production cell-grade is also higher.The 2nd, be raw material with the ore, mainly be with lithionite, triphane is that raw material extracts, present extracting method is sulfuric acid process or vitriolate of tartar and limestone calcination connection, be difficult to remove clean because of the limestone calcination method only adopts in the calcining raw materials impurity such as fluorine, the lithium rate of recovery is also low, the product cost height, as China Patent No. is that ZL85101989 " preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 processing method " carries out high-temperature roasting after vitriolate of tartar and lithionite are mixed by proportioning, 930 ℃ of temperature roastings 2 hours, then the roasting material is carried out two sections level Four extracting technologies and extract lithium carbonate product, this method complex process also causes certain pollution to environment; Number be that it is to be raw material with the lithionite to 201010001287.1 " a kind of methods of extracting lithium from lithionite " also just like Chinese patent application, still only be to adopt calcination mode defluorination extraction process, fluorine is removed unclean, the subsequent disposal difficulty, the lithium yield is not high, so the production cost height, facility investment is big, and the yield of product is low.

Summary of the invention: purpose of the present invention is exactly that a kind of method of extracting Quilonum Retard will be provided, and it is raw material with the lithionite, adopts calcining, acidleach defluorination, extract at low temperature technology, the processing condition gentleness, operating process is stable, with short production cycle, plant factor height, the method that production cost is low.

The present invention is raw material with the lithionite, adopts calcining and the acidleach method that combines, comprise calcining, acidleach, filtration, freezing, separate, concentrated, sinker, it is characterized in that, carry out as follows:

1) calcining defluorination, earlier the lithionite powder is placed rotary kiln in 840 ℃-860 ℃ temperature lower calcination 2-4 hour, and the lithionite after will calcining is crushed to the 250-400 order;

2) acidleach goes out, and the sulphuric acid soln that the lithionite after pulverizing and concentration are 10-30Wt% is by solid-to-liquid ratio 1:3-4 hybrid reaction 3-6 hour, the solid, liquid mixing solutions;

3) filter cleaner is with 2) step solid-liquid mixing solutions, filter with pressure filter, remove filter residue, getting filtrate is mother liquor 1;

4) freezing, separation adds aluminium hydroxide in mother liquor 1, makes solution form K ⁺, Al ³⁺Saturated solution, with saturated solution through freezing, isolate potassium, aluminium, rubidium, cesium alum, after filtration filtrate, mother liquor 2;

5) sinker separates the system product, add liquefied ammonia in mother liquor 2, the Ph of control solution is 3-4, filtering separation slagging-off then, and filter residue carried out washing and filtering, reclaim filtrate, in filtrate, add calcium hydroxide emulsion, through neutralization, concentrated, get concentrated solution, add the sodium carbonate solution reaction in concentrated solution, filter, separate, the solid oven dry is lithium carbonate product, separated filtrate recycling use.

Of the present invention freezing be that secondary is freezing promptly once freezing, be under agitation with mother liquor 1, be cooled to-5～40 ℃, isolate solid rubidium, caesium, potassium, aluminium alum after, filtering separation must be separated filtrate; It is freezing again separating filtrate to be carried out secondary, is separating filtrate under agitation to be cooled to-8～-30 ℃, concentration≤0.2-0.5g/L in the control solution, and filtering separation with cold water thorough washing filter residue, is isolated the solid arcanite, and filtrate is recovered as mother liquor 2.

The method of described extraction Quilonum Retard, preferred 5) step separates, and is after the solid, liquid mixing solutions is detected, Fe in the control solution ³⁺, Mg ²⁺, F ^-, Si ⁴⁺, Ca ²⁺Ionic mass concentration≤0.05% o'clock carries out filtering separation.

Processing step of the present invention is as follows: filler → calcining, defluorination, pulverizing → acidleach → separation → deslagging → freezing → separation → neutralization → separation → concentrate → filtration → sinker.

The present invention adopts calcining and low temperature acidleach defluorination method to extract the Quilonum Retard novel process from the lithionite ore, existing pure high-temperature roasting method, has the processing condition gentleness, operating process is stable, with short production cycle, plant factor height, Quilonum Retard yield height, production cost is low, the production method little to environmental influence.

Utilize Quilonum Retard that the inventive method produces after testing purity reach more than 99.5% technical indicator such as table 1

Li ₂CO ₃	99.5%
		Na ⁺	0.025%
K ⁺	0.001%
		Fe ³⁺	0.002%
Ca ²⁺	0.005%
		Mg ²⁺	0.002%
SO ₄ ^2-	0.05%
		Cl ^-	0.005%
Cu ²⁺	0.001%
		Si	0.005%
H ₂O	0.4%
		Pb+Zn+Al	0.0008%

In the production process of the present invention, the main chemical reactions equation that relates to:

Li ₂O+H ₂SO ₄→Li ₂SO ₄+H ₂O K ₂O+H ₂SO ₄→K ₂SO ₄+H ₂O Na ₂O+H ₂SO ₄→Na ₂SO ₄+H ₂O

Al ₂O ₃+3H ₂SO ₄→AL ₂(SO ₄) ₃+3H ₂O Rb ₂O ₃+3H ₂SO ₄→Rb ₂(SO ₄) ₃+3H ₂O

Cs ₂O+H ₂SO ₄→Cs ₂SO ₄+H ₂O Li ₂SO ₄+?Na ₂CO ₃→LiCO ₃+Na ₂SO ₄

NH ₃+Al ₂(SO ₄) ₃→NH ₄Al(SO ₄) ₂ 。

Embodiment:Describe in detail bright below in conjunction with embodiment furtherly to the present invention.

Relate to concentration among embodiment 1 embodiment and be mass concentration;

Main chemical compositions in the raw material lithionite powder such as following table (wt%)

Li ₂O	K ₂O+ Na ₂O	Al ₂O ₃	SiO ₂	Fe ₂O ₃	Rb ₂O	Cs ₂O	F
								4.0%	8.5%	23.0%	53.57%	0.19%	1.30%	0.20%	4.1%

(1) calcining and acidleach defluorination: filler, lithionite is placed the rotary type stove, in 840-860 ℃ of temperature lower calcination 3 hours,, be crushed to the 250-400 order then to remove most of fluorine; The content of F is about 1.01 wt% in the lithionite powder after testing;

(2) acidleach defluorination is again got the lithionite powder after the pulverizing, by certain solid, liquid mass ratio, adds dilute sulphuric acid and knocks down to boil in the reactor and boil, and constantly stirs in the process of boiling of boiling, fully reaction.Simultaneously the hydrofluoric acid water vapour that contains in the reactor is extracted out, liquefy solution after condensation reclaims;

The processing condition that this step of present embodiment adopts are:

Lithionite and 25% dilute sulphuric acid solid, liquid mass ratio are 1:3;

Temperature of reaction is 120 ℃;

Reaction times is 4h;

(3) filter cleaner is with 2) step solid-liquid mixing solutions, filter with pressure filter, remove filter residue, getting filtrate is mother liquor 1;

(4) freezing, separation adds aluminium hydroxide in mother liquor 1, makes solution form K ⁺, Al ³⁺Saturated solution, with saturated solution through freezing, isolate potassium, rubidium, caesium, aluminium alum mixture, after filtration filtrate, mother liquor 2; It is freezing that this example adopts secondary when freezing, and once freezing is with mother liquor 1, injects refrigerated cylinder, under the agitation condition that does not stop, when temperature is reduced to-5～40 ℃, gets rubidium, caesium, potassium, the mixed solution of aluminium alum.Mixed solution is after separating, and its slag charge is 25 ℃ of cold water washings through temperature, separates solid rubidium, caesium, arcanite, and washing lotion is returned in the mother liquor tank, is washings; Secondary is freezing: with described washings injection last time freezing tank, under the stirring that does not stop, continue to reduce the temperature to-8～-30 ℃, get mother liquor 2;

(5) sinker separates the system product, feeds liquefied ammonia in mother liquor 2, and the Ph value of control solution is 3-4, and the filtering separation slagging-off mainly is an exsiccated ammonium alum then, and filter residue is carried out washing and filtering, reclaims filtrate;

In filtrate, add calcium hydroxide emulsion, through neutralization, concentrate, concentrated solution, in concentrated solution, add the sodium carbonate solution reaction, filter, separate, solids wash, oven dry are lithium carbonate product, separated filtrate recycling use;

The separating controlling that adds calcium hydroxide emulsion should go on foot Fe in the solution ³⁺, Al ³⁺, Mg ²⁺, F, ^εSi ⁴⁺, Ca ²⁺Ionic mass concentration≤0.05% o'clock carries out filtering separation to this solid, liquid mixing solutions.Its slag charge is dried after washing, and reclaims;

Concentrate is to Li with solution concentration ⁺Concentration is 20～45g/L, filters; Solution after the filtration is through recycling once more after treatment.

Claims

1. a method of extracting Quilonum Retard is a raw material with the lithionite, adopts calcining and the acidleach method that combines, comprise calcining, acidleach, filtration, freezing, separate, concentrated, sinker, it is characterized in that, carry out as follows:

4) freezing, separation adds aluminium hydroxide in mother liquor 1, makes solution form K ⁺, Al ³⁺Saturated solution, with saturated solution through freezing, isolate potassium, rubidium, cesium alum, after filtration filtrate, mother liquor 2;

2. according to the method for the described extraction Quilonum Retard of claim 1, it is characterized in that described freezing freezing promptly once freezingly for secondary, be under agitation with mother liquor 1, be cooled to-5～40 ℃, isolate solid rubidium, caesium, arcanite after, filtering separation must be separated filtrate; It is freezing again separating filtrate to be carried out secondary, is separating filtrate under agitation to be cooled to-8～-30 ℃, concentration≤0.2-0.5g/L in the control solution, and filtering separation, the washing filter residue is isolated solid potassium, rubidium, cesium alum, and filtrate is recovered as mother liquor 2.

3. according to the described method of from lithionite, extracting Quilonum Retard of claim 1, it is characterized in that 5) step separates, and is after the solid, liquid mixing solutions is detected, Fe in the control solution ³⁺, Mg ²⁺, F ^-, Si ⁴⁺, Ca ²⁺Ionic mass concentration≤0.05% o'clock carries out filtering separation.