CN101531386B - Method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid - Google Patents
Method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid Download PDFInfo
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- CN101531386B CN101531386B CN2009100643132A CN200910064313A CN101531386B CN 101531386 B CN101531386 B CN 101531386B CN 2009100643132 A CN2009100643132 A CN 2009100643132A CN 200910064313 A CN200910064313 A CN 200910064313A CN 101531386 B CN101531386 B CN 101531386B
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- fluorine
- hydrochloric acid
- containing hydrochloric
- waste slag
- electrolytic aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid, preparing the cryolite product by taking the waste slag of electrolytic aluminium and fluorine-containing hydrochloric acid as materials to react. The method comprises the following advantages: (1), the cheap waste slag of electrolytic aluminium and fluorine-containing hydrochloric acid are taken as the materials for recovering cryolite, which are low in production cost; (2), the fluorine-containing hydrochloric acid is recyclable, thus further lowering the production cost; meanwhile, the fluorine-containing hydrochloric acid treated by lime can be used for preparing calcium chloride; and (3), the cryolite recovered by the invention is qualified for the international standard and can be returned to the electrolytic aluminium industry for reuse.
Description
Technical field
The present invention relates to a kind of method of utilizing fluorine-containing hydrochloric acid from waste slag of electrolytic aluminium, to reclaim sodium aluminum fluoride, belong to the aluminum metal technical field of smelting.
Background technology
At present, Jue Daduoshuo fluoride salt product all is with fluorite (main component CaF
2) be raw material production; the standing stock of fluorite are very limited; grand strategy resource as the development nuclear industry; each state all pays much attention to the protection to fluorite resource; along with deficient day by day, the continuous of price of fluorite resource in the world wide are risen, causing the inorganic fluorine chemical industry to seek other fluorine resources becomes inexorable trend.
Sodium aluminum fluoride is a kind of alkali-metal fluoaluminate, also claims sodium fluoroaluminate, and its molecular formula is Na
3AlF
6,, be mainly used in the fusing assistant of metal smelting aluminium as a kind of Chemicals, also can make the sterilant of farm crop, enamel opacifier, the opalizer and the fusing assistant of glass and enamel production usefulness, the wear-resistant filler of resin rubber also can be used for the production of iron alloy and rimming steel.Along with the fast development of aluminium industry, its potential market share progressively increases, and is also more and more higher to the requirement of quality.
In the Aluminum Electrolysis Production process, for guaranteeing normal production, must make the electrolytic solution in the electrolyzer keep reasonably height and cleanliness factor, therefore need to extract and salvage too much electrolytic solution out swim in electrolytic solution top solid, these solids are just becoming fluorine-containing waste residue through after the condensation.Produce the fluorine-containing waste residue of 10.2 kilograms of one ton of aluminium meeting outputs according to measuring and calculating, it contains the sodium aluminum fluoride more than 30%, aluminum oxide about 1%, calcium oxide about 1%, all the other are pitch carbon granule, carbon element of graphite, aluminium carbide and ferrosilicon oxide compound and other unavoidable impurities, and aluminum oxide fusing point height is difficult to fusing behind the device start, cause ionogen muddy clear, influence the electrolytic aluminum ordinary production.Foreign matter content is too high in these fluorine-containing waste residue, can not reach the standard that is used for electrolytic aluminum of returning by simple purification, and the mode that can only take to pile up is handled, and both environment has been caused pollution like this, also can cause the waste to the fluorine resource simultaneously.
Fluorine-containing hydrochloric acid is the large-tonnage by product of fluorine chemical enterprise, this by-product hydrochloric acid that contains fluorion, because fluorine anion is easy and some melts combine make it dissolving, therefore cause potential safety hazard and accidents such as equipment corrosion, leakage in use easily, and use the fluorine content of back discharging not up to standard, cause the surrounding enviroment fluoride pollution, thereby caused problems such as safety and environmental protection, but also can cause waste the fluorine resource.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing fluorine-containing hydrochloric acid from waste slag of electrolytic aluminium, to reclaim sodium aluminum fluoride, improve the utilization ratio of sodium aluminum fluoride, reduce production costs.
In order to realize above purpose, the technical solution used in the present invention is: a kind of method of utilizing fluorine-containing hydrochloric acid to reclaim sodium aluminum fluoride from waste slag of electrolytic aluminium is that raw material reaction makes the sodium aluminum fluoride product with waste slag of electrolytic aluminium and fluorine-containing hydrochloric acid.
This method specifically comprises the steps:
1. waste slag of electrolytic aluminium is carried out flotation;
2. the fluorine-containing hydrochloric acid that adds 1～15 times of its quality in the waste slag of electrolytic aluminium after flotation was 20～90 ℃ of following stirring reactions 1～6 hour;
3. reaction finishes after-filtration, washes filter cake with water, is drying to obtain the sodium aluminum fluoride product.
The 3. middle washing lotion of filtering resulting filtrate and washing leaching cake of step is collected respectively to recycle.
Described filtrate is adopted the lime treatment discharging.
It is raw material that method of the present invention adopts waste slag of electrolytic aluminium and fluorine-containing hydrochloric acid, reclaims the sodium aluminum fluoride product.At first, waste slag of electrolytic aluminium is carried out flotation handle, the content that detects sodium aluminum fluoride in the waste residue is about 90%, and contains Al and Al about 5%
2O
3, can not directly reclaim; Adopt Al and Al in fluorine-containing hydrochloric acid and the waste slag of electrolytic aluminium again
2O
3Reaction forms sodium aluminum fluoride with the Sodium Fluoride that is dissolved in the fluorine-containing hydrochloric acid then, has therefore improved the content of the sodium aluminum fluoride in the waste residue after the flotation, makes the present invention handle the back sodium aluminum fluoride quality product that is generated and meets international standards, and can satisfy the Aluminium Electrolysis requirement.
In the removal process of sodium aluminum fluoride, Al in the waste slag of electrolytic aluminium and Al
2O
3Combine the sodium aluminum fluoride that generates indissoluble with the fluorine element in the fluorine-containing hydrochloric acid, the fluorine element content in the fluorine-containing hydrochloric acid that participates in reacting decreases, and has weakened fluorine-containing hydrochloric acid in use to the corrosion of equipment, has improved the utilization ratio of fluorine-containing hydrochloric acid; The filtrate that the reaction after-filtration obtains is used to make calcium chloride through lime treatment, residual fluorine element can also be removed simultaneously, and the filtrate after the processing has reached emission standards, has prevented because of discharging pollution on the environment not up to standard and destruction.
Method advantage provided by the present invention is: 1. waste slag of electrolytic aluminium and the fluorine-containing hydrochloric acid with cheapness is that raw material reclaims sodium aluminum fluoride, and production cost is low; 2. the repeated use capable of circulation of fluorine-containing hydrochloric acid has further reduced production cost, utilizes the reacted fluorine-containing hydrochloric acid acid solution of lime treatment to be used to prepare calcium chloride simultaneously; 3. the sodium aluminum fluoride that the inventive method reclaimed, its quality meets international standards, can return aluminum electrolysis industry and continue to use, and the result is as shown in table 1 in its mass analysis.
Table 1 utilizes the mass analysis result such as the following table of the resulting sodium aluminum fluoride product of the present invention
Embodiment
Embodiment 1
The method that present embodiment utilizes fluorine-containing hydrochloric acid to reclaim sodium aluminum fluoride from waste slag of electrolytic aluminium comprises the steps:
1. waste slag of electrolytic aluminium is carried out flotation;
2. the fluorine-containing hydrochloric acid that adds 1 times of its quality in the waste slag of electrolytic aluminium after flotation was 20 ℃ of following stirring reactions 6 hours;
3. reaction finishes after-filtration, washes filter cake with water, and filtration cakes torrefaction is promptly obtained the sodium aluminum fluoride product.
Embodiment 2
The method of utilizing fluorine-containing hydrochloric acid to reclaim sodium aluminum fluoride from waste slag of electrolytic aluminium of present embodiment comprises the steps:
1. waste slag of electrolytic aluminium is carried out flotation;
2. the fluorine-containing hydrochloric acid that adds 8 times of its quality in the waste slag of electrolytic aluminium after flotation was 55 ℃ of following stirring reactions 3.5 hours;
3. reaction finishes after-filtration, washes filter cake with water, and filtration cakes torrefaction is promptly obtained the sodium aluminum fluoride product.
Embodiment 3
The method of utilizing fluorine-containing hydrochloric acid to reclaim sodium aluminum fluoride from waste slag of electrolytic aluminium of present embodiment comprises the steps:
1. waste slag of electrolytic aluminium is carried out flotation;
2. the fluorine-containing hydrochloric acid that adds 15 times of its quality in the waste slag of electrolytic aluminium after flotation was 90 ℃ of following stirring reactions 1 hour;
3. reaction finishes after-filtration, washes filter cake with water, and filtration cakes torrefaction is promptly obtained the sodium aluminum fluoride product.
The 3. middle washing lotion of filtering resulting filtrate and washing leaching cake of the step of present embodiment 1-3 is collected respectively, and the filtrate of collection is recycled and reused for and participates in reaction production sodium aluminum fluoride, and the washing lotion of collection is recycled and reused for washing leaching cake.When filtrate cycle is used certain number of times, adopt the lime treatment discharging.
Claims (4)
1. method of utilizing fluorine-containing hydrochloric acid from waste slag of electrolytic aluminium, to reclaim sodium aluminum fluoride, it is characterized in that: with waste slag of electrolytic aluminium and fluorine-containing hydrochloric acid is that raw material reaction makes the sodium aluminum fluoride product, wherein the consumption of fluorine-containing hydrochloric acid be the waste slag of electrolytic aluminium quality 1-15 doubly, the condition of reaction is 20～90 ℃ of following stirring reactions 1～6 hour.
2. the method for utilizing fluorine-containing hydrochloric acid to reclaim sodium aluminum fluoride from waste slag of electrolytic aluminium according to claim 1, it is characterized in that: this method specifically comprises the steps:
1. waste slag of electrolytic aluminium is carried out flotation;
2. the fluorine-containing hydrochloric acid that adds 1～15 times of its quality in the waste slag of electrolytic aluminium after flotation was 20～90 ℃ of following stirring reactions 1～6 hour;
3. reaction finishes after-filtration, washes filter cake with water, is drying to obtain the sodium aluminum fluoride product.
3. the method for utilizing fluorine-containing hydrochloric acid to reclaim sodium aluminum fluoride from waste slag of electrolytic aluminium according to claim 2 is characterized in that: the 3. middle washing lotion of filtering resulting filtrate and washing leaching cake of step is collected respectively to recycle.
4. the method for utilizing fluorine-containing hydrochloric acid to reclaim sodium aluminum fluoride from waste slag of electrolytic aluminium according to claim 3 is characterized in that: described filtrate is adopted the lime treatment discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100643132A CN101531386B (en) | 2009-03-03 | 2009-03-03 | Method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100643132A CN101531386B (en) | 2009-03-03 | 2009-03-03 | Method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid |
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| Publication Number | Publication Date |
|---|---|
| CN101531386A CN101531386A (en) | 2009-09-16 |
| CN101531386B true CN101531386B (en) | 2011-02-02 |
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| CN2009100643132A Expired - Fee Related CN101531386B (en) | 2009-03-03 | 2009-03-03 | Method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219249A (en) * | 2011-05-14 | 2011-10-19 | 多氟多化工股份有限公司 | Production method of cryolite |
| CN102389891A (en) * | 2011-09-30 | 2012-03-28 | 巨锋 | Electrolytic aluminum anode waste separating and recovering method |
| CN102583478A (en) * | 2012-02-26 | 2012-07-18 | 张炜铭 | Recycling method of waste hydrochloric acid containing aluminum |
| CN103193256B (en) * | 2013-04-25 | 2014-06-18 | 陈俊良 | Method for synchronously recycling cryolite and carbon powder from electrolytic aluminum waste residue |
| CN105502453B (en) * | 2016-01-14 | 2017-01-25 | 李国法 | Production process for conducting flotation and drying on regenerative cryolite |
| CN106745138A (en) * | 2017-02-27 | 2017-05-31 | 中南大学 | A kind of use HCl HF mixed gas production hexafluoro sodium aluminate and the method for reclaiming HCl |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2186433A (en) * | 1936-11-17 | 1940-01-09 | Firm Rutgerswerke Ag | Process for the recovery of aluminum and fluorine compounds from the worn-out linings of the electric furnaces employed for the production of aluminum |
| CN1358581A (en) * | 2001-11-20 | 2002-07-17 | 舒大平 | Harmless treatment and comprehensive utilization method for aluminium electrolytic carbon slag and waste cathode material |
-
2009
- 2009-03-03 CN CN2009100643132A patent/CN101531386B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2186433A (en) * | 1936-11-17 | 1940-01-09 | Firm Rutgerswerke Ag | Process for the recovery of aluminum and fluorine compounds from the worn-out linings of the electric furnaces employed for the production of aluminum |
| CN1358581A (en) * | 2001-11-20 | 2002-07-17 | 舒大平 | Harmless treatment and comprehensive utilization method for aluminium electrolytic carbon slag and waste cathode material |
Non-Patent Citations (1)
| Title |
|---|
| 康宁.铝电解废渣的浮选.《有色冶金节能》.2004,第21卷(第1期),30-32. * |
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