CN101307470A - Method for preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes - Google Patents
Method for preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes Download PDFInfo
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- CN101307470A CN101307470A CNA2008101154586A CN200810115458A CN101307470A CN 101307470 A CN101307470 A CN 101307470A CN A2008101154586 A CNA2008101154586 A CN A2008101154586A CN 200810115458 A CN200810115458 A CN 200810115458A CN 101307470 A CN101307470 A CN 101307470A
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Abstract
The invention relates to a method for preparing an additive for aluminum electrolysis electrolytes by lithium-containing wastes. The method is characterized in that in the preparation process, the lithium-containing wastes after being smashed undergo acid dissolution, alkalization iron removal, alkalization aluminum removal and alkalization cobalt removal, the wastes are added with carbonates for precipitation reaction, and the lithium carbonates are obtained by filtering and separation, and are dried to be used as the additive for aluminum electrolysis electrolytes. The method of the invention has the advantages that the scale of production can be conveniently adjusted and raw materials are good in adaptability, and simultaneously the product of the invention is a complex additive of a plurality of substances, thereby reducing technological process, lowering technological requirement, greatly lowering manufacturing cost and improving recovery of resources; compared with the prior process for preparing the additive for aluminum electrolysis electrolytes by directly utilizing carbonates and fluoride salts, the technical proposal of the invention has the advantages of cheap material, resource conservation, cyclic utilization of resources, short technological process, simple operation and high recovery ratio.
Description
Technical field
The present invention relates to a kind of method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes.
Background technology
Electrolysis of aluminum adopts traditional Hall-Hoult processing method to produce always, and ionogen also all uses sodium cryolite base fluorochemical.Though the sodium cryolite electrolyte system has advantages such as current efficiency height, alumina dissolution degree be big, has the electrolysis temperature height, problem such as energy consumption is big.Mainly be to add small amount of alkali metal or alkaline-earth metal fluoride or carbonate as additive in producing at present, particularly lithium fluoride and Quilonum Retard reduce electrolysis temperature to reach, improve electric conductivity and reduce the purpose of energy consumption.But, influence large-scale industrial application because it is higher to use lithium salts additive unit cost.
Along with the fast development, the particularly development of portable power-equipment such as mobile phone, electromobile and popularization and application of electronic industry, lithium salts turnout and consumption are how much numbers and increase in recent years.But, the various solid waste that contain lithium have also unavoidably appearred in production and use, and this effectively utilizes for resources circulation and has proposed new problem.
The main processing mode that contains the lithium solid waste at present is mainly by acid molten back extraction or electrodeposition and extracts the recovery technology of carrying out sinker behind the solution that cobalt obtains being rich in lithium; Other has high-temperature roasting to remove fluorine-containing binding agent and carbon, the heavy aluminium of selectivity to obtain recovery technology and the organic solvent dissolution binding agent that carries out purifying behind the solid-state cobalt acid lithium, and the technology of cobalt, lithium, aluminium, copper is reclaimed in classification.The ubiquitous problem of these technologies is the technical process complexity, and organic efficiency is low, and cost recovery is big, and also there is hidden danger in the aspect of environment protection simultaneously.
The major cause that these problems occur is the organic fluorine of bringing in metallic impurity such as the aluminium that contain different amounts in the waste, iron, copper, calcium, sodium, potassium and carbon, silicon and the binding agent, must possess corresponding working procedures and carry out removal of impurities or separation and purification, purifying, it is also quite high to require.Preparation used for aluminium electrolysis additive then need not to remove sodium, potassium, calcium, magnesium, aluminium, fluorine, because of these elements are a large amount of appearance in additive or the ionogen, only need allocate getting final product according to the finished product chemical ingredients.And carbon, iron, silicon also enter electrolyzer from other approach, need not thoroughly to remove in additive agent electrolyte, only need guarantee that the content of these impurity does not influence the normal operation of electrolysis of aluminum, and purifying requires and the technological operation difficulty greatly reduces.Hot environment and fluorochemical gathering system are very effective to the processing of organic fluorine in the electrolysis of aluminum in addition, simplify technical process.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, and the usefulness that it is characterized in that providing a kind of rich and easy to get, low price of originating, do not have secondary pollution, technical process is simple, production cost is low, resource recovery is high contains the method that the lithium solid waste prepares additive agent electrolyte for electrolyzing aluminium.
The objective of the invention is to be achieved through the following technical solutions.
With the method for preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes, it is characterized in that its preparation process comprises:
(1) will contain the fragmentation of lithium waste;
(2) broken thing is added in the strong acid (being advisable with sulfuric acid and hydrochloric acid), carry out sour molten after-filtration;
(3) in filtrate, add sodium bicarbonate, behind the heavy iron of reaction; Filter to isolate ironic hydroxide;
(4) with hydro-oxidation sodium in the filtrate of step (3), behind the heavy aluminium of reaction; Filter to isolate aluminium hydroxide;
(5) filtrate with step (4) adds sodium oxalate, behind the heavy cobalt of reaction; Filter to isolate cobalt oxalate;
(6) in the filtrate of step (5), add the yellow soda ash reaction precipitation after; The filtering separation Quilonum Retard;
(7) will separate the matter additive do electrolysis of aluminum after the filtering separation Quilonum Retard drying.
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention is characterized in that being crushed to below the granularity 500 μ m containing the lithium waste.
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention is characterized in that the molten condition of described acid is 80 ℃ of temperature, and acid concentration is 10mol/l, 2 hours reaction times.
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention, it is characterized in that described deferrization process control condition be pH 2～3,70～90 ℃ of temperature add oxygenant or air blast and stir ageing 1 hour.
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention is characterized in that described aluminium process control condition: the pH of removing 4～5,70～90 ℃ of temperature, digestion time 3 hours;
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention is characterized in that described cobalt process control condition: the pH of removing 8～9,60～80 ℃ of temperature, digestion time 2 hours;
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention is characterized in that described carbon alkali sinker process control condition: yellow soda ash is excessive 10%～20%, 50～70 ℃ of temperature of reaction, 3 hours reaction times;
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention, the drying temperature that it is characterized in that described carbon alkali sinker is 450 ℃, 2 hours time of drying.
Method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes of the present invention is characterized in that main depleting substance is a waste in the industrial production, and its raw material sources are abundant, low price, can reach good environment and social benefit simultaneously.
Method of the present invention, it contains in the discarded energy industry of lithium solid and contains the mainly lithium cell to scrap of lithium waste, is characterized in containing multiple valuable metal, need carry out comprehensive reutilization.Therefore, required production is reclaimed technology than other processing scheme complexity.
Method of the present invention, processing contain the lithium solid waste after also may obtain following byproduct: ironic hydroxide, aluminium hydroxide and cobalt oxalate etc.The production desired raw material is hydrochloric acid (or sulfuric acid), sodium hydroxide, sodium oxalate, sodium bicarbonate and yellow soda ash, and it is rich and easy to get to originate, low price, and what discharge flow process at last is sodium-chlor (or sodium sulfate), can utilize commercially available or again, does not have secondary pollution.The present invention can be made full use of lithium primary recovery:＞50% the most with containing the lithium waste resource; Lithium loops back yield:＞95%, have very big market outlook.
Method of the present invention, industrial scale is easy to adjust, and the raw material adaptive faculty is strong.Be the composite additive of multiple material because of product of the present invention simultaneously, the original processing method that contains the lithium waste that reclaims of contrast reduces technical process, reduces processing requirement, significantly reduces production cost, improves resource recovery.Original carbonate and the fluoride salt of directly using of contrast prepared the technology of additive agent electrolyte for electrolyzing aluminium, and it is cheap that technical matters scheme of the present invention has a raw material, economizes on resources, realize the advantage that resource circulation is utilized, technical process is short, and is simple to operate, rate of recovery advantage of higher.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
With the method for preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes, its preparation process comprises: (1) will contain the fragmentation of lithium waste; (2) broken thing is added in the sulfuric acid, carry out sour molten after-filtration; (3) in filtrate, add sodium bicarbonate, behind the heavy iron of reaction; Filter to isolate ironic hydroxide; (4) add sodium hydroxide in the filtrate with step (3), behind the heavy aluminium of reaction; Filter to isolate aluminium hydroxide; (5) with the filtrate mesoxalic acid sodium of step (4), reaction is sunk behind the cobalt; Filter to isolate cobalt oxalate; (6) in the filtrate of step (5), add the yellow soda ash reaction precipitation after; The filtering separation Quilonum Retard; (7) will separate the matter additive do electrolysis of aluminum after the filtering separation Quilonum Retard drying.
Embodiment
Certain cobalt acid lithium is the useless battery of mobile phone of electrode active material, and main foreign metal is iron, aluminium, cobalt, nickel, copper etc., and inorganics is carbon, silicon, boron, phosphorus etc.Through chemical analysis, typical composition is as follows: cobalt: about 42%, lithium: 5%, aluminium: 11%, oxygen: 32%, carbon, silicon, other: 10%.
The main technique condition:
The molten condition of acid: 80 ℃ of temperature, acid concentration are 10mol/l, 2 hours reaction times;
Deferrization process condition: pH is 2～3, and 70～90 ℃ of temperature add oxygenant or air blast and stir ageing 1 hour;
Remove aluminium processing condition: pH 4～5,70～90 ℃ of temperature, digestion time 3 hours;
Remove cobalt processing condition: pH 8～9,60～80 ℃ of temperature, digestion time 2 hours;
Carbon alkali sinker processing condition: yellow soda ash is excessive 10～20%, 50～70 ℃ of temperature of reaction, 3 hours reaction times;
Dry: 450 ℃ of drying temperatures, 2 hours time of drying.
The molten rate of recovery of acid reaches more than 98%, and iron ion content is below 0.1% after the removal of impurities, and aluminium composition is below 0.1%, and cobalt purity can reach more than 98% in the cobalt oxalate.
Claims (8)
1. with the method for preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes, it is characterized in that its preparation process comprises:
(1) will contain the fragmentation of lithium waste;
(2) broken thing is added in the inorganic acid fluid, carry out sour molten after-filtration;
(3) in filtrate, add sodium bicarbonate, after the reaction deironing; Filter to isolate ironic hydroxide;
(4) with hydro-oxidation sodium in the filtrate of step (3), after reaction removes aluminium; Filter to isolate aluminium hydroxide;
(5) add sodium oxalate in the filtrate with step (4), after reaction removes cobalt; Filter to isolate cobalt oxalate;
(6) in the filtrate of step (5), add the yellow soda ash reaction precipitation after; The filtering separation Quilonum Retard;
(7) will separate the matter additive do electrolysis of aluminum after the filtering separation Quilonum Retard drying.
2. the method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes according to claim 1 is characterized in that being crushed to below the granularity 500 μ m containing the lithium waste.
3. the method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes according to claim 1 is characterized in that the molten condition of described acid is 80 ℃ of temperature, and acid concentration is 10mol/l, 2 hours reaction times.
4. the method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes according to claim 1, it is characterized in that described deferrization process condition be pH 2～3,70～90 ℃ of temperature add oxygenant or air blast and stir ageing 1 hour.
5. the method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes according to claim 1 is characterized in that described aluminium processing condition: the pH of removing 4～5,70～90 ℃ of temperature, digestion time 3 hours;
6. the method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes according to claim 1 is characterized in that described cobalt processing condition: the pH of removing 8～9,60～80 ℃ of temperature, digestion time 2 hours;
7. the method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes according to claim 1 is characterized in that described carbon alkali sinker processing condition: yellow soda ash is excessive 10%～20%, 50～70 ℃ of temperature of reaction, 3 hours reaction times;
8. the method with preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes according to claim 1, the drying temperature that it is characterized in that described carbon alkali sinker is 450 ℃, 2 hours time of drying.
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| CNA2008101154586A CN101307470A (en) | 2008-06-24 | 2008-06-24 | Method for preparing additive agent electrolyte for electrolyzing aluminium from lithium-containing wastes |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492962A (en) * | 2011-12-28 | 2012-06-13 | 株洲科能新材料有限责任公司 | Preparation method for tellurium electrolyte |
| CN102515203A (en) * | 2011-11-16 | 2012-06-27 | 多氟多化工股份有限公司 | Processing method of wastes produced when battery grade lithium fluoride is manufactured by adopting carbonization method |
| CN104313642A (en) * | 2014-11-17 | 2015-01-28 | 中南大学 | Method for reducing voltage drop of aluminum electrolysis anode gas film |
| CN108569711A (en) * | 2018-05-22 | 2018-09-25 | 河南科技大学 | The method that lithium salts prepares lithium carbonate is extracted from aluminium electroloysis high-lithium electrolyte waste |
| CN111547775A (en) * | 2020-05-14 | 2020-08-18 | 湖北中环新材料科技有限公司 | Method for preparing high-purity hydroxide by recycling waste lithium batteries |
-
2008
- 2008-06-24 CN CNA2008101154586A patent/CN101307470A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515203A (en) * | 2011-11-16 | 2012-06-27 | 多氟多化工股份有限公司 | Processing method of wastes produced when battery grade lithium fluoride is manufactured by adopting carbonization method |
| CN102515203B (en) * | 2011-11-16 | 2013-12-11 | 多氟多化工股份有限公司 | Processing method of wastes produced when battery grade lithium fluoride is manufactured by adopting carbonization method |
| CN102492962A (en) * | 2011-12-28 | 2012-06-13 | 株洲科能新材料有限责任公司 | Preparation method for tellurium electrolyte |
| CN104313642A (en) * | 2014-11-17 | 2015-01-28 | 中南大学 | Method for reducing voltage drop of aluminum electrolysis anode gas film |
| CN108569711A (en) * | 2018-05-22 | 2018-09-25 | 河南科技大学 | The method that lithium salts prepares lithium carbonate is extracted from aluminium electroloysis high-lithium electrolyte waste |
| CN111547775A (en) * | 2020-05-14 | 2020-08-18 | 湖北中环新材料科技有限公司 | Method for preparing high-purity hydroxide by recycling waste lithium batteries |
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Open date: 20081119 |