CN105152188A - Method for preparing lithium carbonate and potassium sulfate by using zinnwaldite - Google Patents
Method for preparing lithium carbonate and potassium sulfate by using zinnwaldite Download PDFInfo
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- CN105152188A CN105152188A CN201510477466.5A CN201510477466A CN105152188A CN 105152188 A CN105152188 A CN 105152188A CN 201510477466 A CN201510477466 A CN 201510477466A CN 105152188 A CN105152188 A CN 105152188A
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- zinnwaldite
- potassium
- potassium sulfate
- filtrate
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Abstract
The invention discloses a method for preparing lithium carbonate and potassium sulfate by using zinnwaldite. The method comprises the following steps of: (1) acid dissolution and decomposition of zinnwaldite; (2) impurity removal of a filtrate resulting from acid dissolution; (3) crystallization of potassium sulfate; and (4) precipitation of lithium carbonate. The method is short in technical process, mild in reaction condition, and low in energy consumption, and is free of high-temperature calcination. Two important elements of lithium and potassium are extracted from zinnwaldite, thereby realizing comprehensive utilization of resources.
Description
Technical field
The present invention relates to a kind of method of zinnwaldite comprehensive utilization of resources, particularly utilize zinnwaldite to prepare the method for Quilonum Retard and potassium sulfate.
Technical background
With the anxiety of world energy supplies, lithium electricity new forms of energy are one of important industry of current new forms of energy development, Quilonum Retard is as the base mateiral of lithium electricity New Energy Industry, there is larger development prospect, Quilonum Retard is also a kind of important industrial chemicals simultaneously, is widely used in the fields such as glass, pottery, semiconductor laser material, lubricating grease.Zinnwaldite is a kind of important in lithium minerals, and the main method extracting Quilonum Retard at present from lithionite has: limestone sintering process, sulfatizing roasting method, chlorinating roasting, basic pressure digestion method and pickling process (patent of invention: 201210240882.X and application for a patent for invention: 201110075325.2).High-temperature sintering process energy consumption is high, and logistics capacity is large; During the reaction of pressure cooking method, temperature, pressure is large, high to equipment requirements; Pickling process is simple to operate, easy control of process conditions, but uses pickling process process lithionite at present, only extracts Quilonum Retard wherein, have ignored the comprehensive utilization of other elements, cause the waste of resource.
Summary of the invention
The invention provides one utilizes zinnwaldite to prepare Quilonum Retard, simultaneously the method for reclaim(ed) sulfuric acid potassium.The technical scheme that the present invention takes is:
Utilize zinnwaldite to prepare a method for Quilonum Retard and potassium sulfate, it is characterized in that, comprise the following steps:
(1) the acid-soluble decomposition of zinnwaldite: mixed to the sulfuric acid that 120-200 object zinnwaldite and concentration are 6.1-7.5mol/L by grinding and be placed in acidification reactor, react 3-6h under heated and stirred, after reaction terminates, filters and obtains acid-soluble filtrate;
(2) acid-soluble filtrate removal of impurities: drip potassium hydroxide solution in acid-soluble filtrate, until filtrate pH value is 5-6, crosses and filters iron ion and aluminum ion, be purified filtrate;
(3) potassium sulfate crystallization: purifying filter liquor evaporation concentration is separated out to there being potassium sulfate crystal, and be cooled to 0-10 DEG C, filter to isolate potassium sulfate, drying obtains potassium product, filtrate is rich lithium solution; Li in rich lithium solution
+concentration is greater than 25g/L.
(4) Quilonum Retard precipitation: add solution of potassium carbonate in rich lithium solution, stirring reaction 1-2h under 80-100 DEG C of condition, filtering separation, solid is lithium carbonate product, and filtrate returns the purifying filter liquor in step (3).
Zinnwaldite in step (1) and sulfuric acid mass ratio are 1: 2-1: 4, and acid-soluble temperature is 140-160 DEG C, and the rate of decomposition of zinnwaldite reaches 98%.
In step (2), the concentration of potassium hydroxide solution is 6-10mol/L.
Solution of potassium carbonate concentration is 7-9mol/L in step (4), rich lithium solution with add solution of potassium carbonate volume ratio and be: 7-9.
Advantage of the present invention:
The present invention adopts sulfuric acid decomposition zinnwaldite, decomposes filtrate and uses potassium hydroxide solution adjusted to ph, and removing iron and aluminum ions, purifying filter liquor evaporative crystallization goes out potassium product, then adds solution of potassium carbonate and is settled out Quilonum Retard.The present invention is extracted lithium and potassium two kinds of elements in zinnwaldite simultaneously, and resource utilization is high, greatly reduce the production cost of Quilonum Retard, and technical process is simple.
Accompanying drawing explanation
Fig. 1 is the process flow sheet utilizing zinnwaldite to prepare Quilonum Retard and potassium sulfate.
Fig. 2 is X-ray powder diffraction result.
Embodiment
Fig. 1 is the process flow sheet utilizing zinnwaldite to prepare Quilonum Retard and potassium sulfate.As shown in Figure 1, zinnwaldite is after the acid of sulfuric acid is invaded, after being separated by filtration again, obtain acid-soluble filtrate and acid-soluble filter residue, acid-soluble filtrate is through the removal of impurities of solution of potassium carbonate, after being separated by filtration again, be purified filtrate and filter residue, filter residue, after hot wash, obtains washery slag and wash water, wash water together with purifying filter liquor evaporation concentration, cooling be separated by filtration again after, obtain potassium product and rich lithium solution, in rich lithium solution, add solution of potassium carbonate, be separated by filtration, obtain lithium carbonate product, filtrate returns step (3) and uses as purifying filter liquor.
Embodiment
The chemical composition analysis result of zinnwaldite (BR-1) is as table 1, grinding is mixed to the sulfuric acid 400g that-200 object zinnwaldite 100g and concentration are 6.4mol/L and is placed in acidification reactor, under agitation condition, be heated to 140 DEG C, reaction 4h, after reaction terminates, filtering separation obtains acid-soluble filtrate; In acid-soluble filtrate, drip the potassium hydroxide solution of 6mol/L, until filtrate pH value is 5-6, crosses and filter iron ion and aluminum ion, be purified filtrate; Purifying filter liquor evaporation concentration is separated out to there being potassium sulfate crystal, is cooled to 0 DEG C, filters to isolate potassium sulfate, drying obtains potassium product (KS-1), and its chemical composition analysis result, as table 2, meets agricultural potassium sulfate premium grads standard, filtrate is rich lithium solution, wherein, and Li in rich lithium solution
+concentration is 28g/L40mL; In rich lithium solution, add the solution of potassium carbonate 5.3mL of 8mol/L, stirring reaction 1-2h under 90 DEG C of conditions, thickening filtration, solid is lithium carbonate product (LC-1), and filtrate returns the purifying filter liquor in step (3).The chemical composition analysis result of lithium carbonate product (LC-1) is as shown in table 3, and X-ray powder diffraction result as shown in Figure 2, meets Li in technical grade Quilonum Retard GB/T11075-2003
2cO
3the requirement of-0.
Chemical composition analysis result (the w of table 1 zinnwaldite
b%)
Chemical composition analysis result (the w of table 2 potassium product
b%)
Chemical composition analysis result (the w of table 3 Quilonum Retard
b%)
Claims (4)
1. utilize zinnwaldite to prepare a method for Quilonum Retard and potassium sulfate, comprise the following steps:
(1) the acid-soluble decomposition of zinnwaldite: mixed to the sulfuric acid that 120-200 object zinnwaldite and concentration are 6.1-7.5mol/L by grinding and be placed in acidification reactor, react 3-6h under heated and stirred, after reaction terminates, filters and obtains acid-soluble filtrate;
(2) acid-soluble filtrate removal of impurities: drip potassium hydroxide solution in acid-soluble filtrate, until filtrate pH value is 5-6, crosses and filters iron ion and aluminum ion, be purified filtrate;
(3) potassium sulfate crystallization: purifying filter liquor evaporation concentration is separated out to there being potassium sulfate crystal, and be cooled to 0-10 DEG C, filter to isolate potassium sulfate, drying obtains potassium product, filtrate is rich lithium solution; Li in rich lithium solution
+concentration is greater than 25g/L.
(4) Quilonum Retard precipitation: add solution of potassium carbonate in rich lithium solution, stirring reaction 1-2h under 80-100 DEG C of condition, filtering separation, solid is lithium carbonate product, and filtrate returns the purifying filter liquor in step (3).
2. a kind of method utilizing zinnwaldite to prepare Quilonum Retard and potassium sulfate as claimed in claim 1, it is characterized in that, zinnwaldite in step (1) and sulfuric acid mass ratio are 1: 3-1: 4, and acid-soluble temperature is 140-160 DEG C, and the rate of decomposition of zinnwaldite reaches 98%.
3. a kind of method utilizing zinnwaldite to prepare Quilonum Retard and potassium sulfate as claimed in claim 1, is characterized in that, in step (2), the concentration of potassium hydroxide solution is 6-10mol/L.
4. a kind of method utilizing zinnwaldite to prepare Quilonum Retard and potassium sulfate as claimed in claim 1, is characterized in that, in step (4), solution of potassium carbonate concentration is 7-9mol/L, Li in rich lithium solution
+concentration is for being greater than 25g/L; Rich lithium solution with add solution of potassium carbonate volume ratio and be: 7-9.
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| CN201510477466.5A CN105152188A (en) | 2015-08-06 | 2015-08-06 | Method for preparing lithium carbonate and potassium sulfate by using zinnwaldite |
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| CN201510477466.5A CN105152188A (en) | 2015-08-06 | 2015-08-06 | Method for preparing lithium carbonate and potassium sulfate by using zinnwaldite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044804A (en) * | 2016-05-26 | 2016-10-26 | 四川思达能环保科技有限公司 | Novel process for producing lithium salt by aid of sulfuric acid methods |
| CN110342551A (en) * | 2019-08-27 | 2019-10-18 | 江西安德力高新科技有限公司 | It is a kind of using lepidolite as the lithium carbonate production system of raw material |
| CN114634355A (en) * | 2022-03-11 | 2022-06-17 | 苏州大学 | Treatment method for recycling ferrous lepidolite leaching residues |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044804A (en) * | 2016-05-26 | 2016-10-26 | 四川思达能环保科技有限公司 | Novel process for producing lithium salt by aid of sulfuric acid methods |
| CN110342551A (en) * | 2019-08-27 | 2019-10-18 | 江西安德力高新科技有限公司 | It is a kind of using lepidolite as the lithium carbonate production system of raw material |
| CN110342551B (en) * | 2019-08-27 | 2022-02-18 | 江西金德锂新能源科技有限公司 | Lithium carbonate production system using lepidolite as raw material |
| CN114634355A (en) * | 2022-03-11 | 2022-06-17 | 苏州大学 | Treatment method for recycling ferrous lepidolite leaching residues |
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Application publication date: 20151216 |
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