CN101239731A - Method for producing cryolite from aluminum electrolysis waste slag - Google Patents
Method for producing cryolite from aluminum electrolysis waste slag Download PDFInfo
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- CN101239731A CN101239731A CNA2008100307813A CN200810030781A CN101239731A CN 101239731 A CN101239731 A CN 101239731A CN A2008100307813 A CNA2008100307813 A CN A2008100307813A CN 200810030781 A CN200810030781 A CN 200810030781A CN 101239731 A CN101239731 A CN 101239731A
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Abstract
The present invention provides a method of cryolite by aluminum electrolysis waste residue, aluminium electrolysis waste residue is milled below 60-200 mesh, removing carbon, iron in waste residue, adding concentrated sulphuric acid, reacting 30-180 min under the temperature 20-90 Celsius, the prepared Hydrogen fluoride gas is absorbed by water or lye. Adding 1-20 times water of waste quality after completing, mixing 2-20 min, filtering, adding 10%-30% sodium carbonate solution or solid sodium carbonate, 10%-50% hydrofluoric acid in filtering liquid. Under the mixing condition, ice crystal stone slurry is obtained by reaction 1-3 hours under the temperature 20-95 Celsius, ice crystal stone product is obtained by filtering, washing, drying. The invention can utilize waste slag generated in aluminium electrolysis course, and has lower cost, hydrogen fluoride gas generated in the waste treating process produces ice crystal stone product for recycling use after being absorbed by water or lye.
Description
Technical field
The invention belongs to a kind of preparation method of sodium aluminum fluoride, particularly a kind of method of utilizing producing cryolite from aluminum electrolysis waste slag.
Background technology
Sodium aluminum fluoride is an indispensable fusing assistant during aluminium metallurgy is produced, also can do the opalizers of sterilant, enamel opacifier, glass and enamel production usefulness of farm crop and fusing assistant, resin rubber wear-resisting, also can be used for the electrolytic solution of aluminium alloy, iron alloy and rimming steel and the batching of emery wheel etc.At present the method for domestic production cryolith mainly contains the hydrofluoric acid method: can branch dry method and wet method, dry method be with the gaseous hydrogen fluoric acid 400～700 ℃ and aluminium hydroxide reaction, generate hydrofluoaluminic acid, generate in pyroreaction with soda ash then.Wet method is will to add soda ash again after 40～60% hydrofluoric acid and the aluminium hydroxide reaction and make.The silicofluoric acid method: can divide Neutral ammonium fluoride intermediate product and Sodium Silicofluoride intermediate product method, the former generates with the sodium aluminate reaction after silicofluoric acid and the ammoniacal liquor ammonification again.The latter be with the waste gas containing fluoride in the production of phosphate fertilizer after reclaiming Sodium Silicofluoride, make through operations such as ammonification are synthetic again.Carbonation method: in sodium aluminate and Fluorinse, pass to carbonic acid gas, also can make sodium aluminum fluoride.The Aluminium industry absorption method: the diluted hydrofluoric acid and the sodium aluminate that reclaim from the waste gas that aluminium metallurgy is produced react recyclable sodium aluminum fluoride.Also has clay bittern method (CN1056091A) in addition: obtain liquor alumini chloridi with hydrochloric acid and clay reaction, add salt and hydrofluoric acid again and react at normal temperatures and pressures and obtain sodium aluminum fluoride.Above method exists contaminate environment more serious, prices of raw and semifnished materials costliness, shortcomings such as production cost height.Therefore, if utilize waste residue to produce sodium aluminum fluoride reducing production costs, to turn waste into wealth simultaneously, but the production of sodium aluminum fluoride provides new approach.Many relevant patent applications reports have been arranged aspect acid waste residue (main component the is an ammonium aluminum fluoride) synthetic cryolite utilizing aluminium shape surface to handle.CN1456507 provides a kind of method of producing sodium aluminum fluoride, is the raw material production sodium aluminum fluoride with ammonium aluminum fluoride and soda ash, and its ammonium aluminum fluoride is taken from aluminium shape surface and handled waste residue, is acid waste residue.It is the method for feedstock production sodium aluminum fluoride with acid etching aluminium slag ammonium aluminum fluoride and sodium aluminate that CN1868888A provides a kind of, and it is the feedstock production sodium aluminum fluoride that CN1868887A adopts ammonium aluminum fluoride, Tai-Ace S 150 and saltcake.It is the method for feedstock production sodium aluminum fluoride with acid etching aluminium slag, sodium-chlor, hydrofluoaluminic acid that CN153978A (Appl.03128411.6) discloses a kind of.But more than adopting acid fluorine-containing aluminium slag is that raw material (ammonium aluminum fluoride) prepares sodium aluminum fluoride, and its dimension-limited is in this acid waste residue amount quantity.Because handle the used ammonium bifluoride of aluminium shape surface, the cost that prices such as hydrofluoric acid are higher, cause handling aluminium section bar is higher, so the acid waste residue amount quantity that this acidic process aluminium section bar produces is very limited.
Along with the development of aluminium electrolytic industry, the consumption of sodium aluminum fluoride is grown with each passing day, also produce a large amount of electrolysis of aluminum waste residues simultaneously, contain a large amount of sodium aluminum fluorides in these electrolysis of aluminum waste residues, but, have a strong impact on current efficiency, so can not be directly used in electrolysis of aluminum because contain a large amount of charcoals and other impurity.Therefore, utilize producing cryolite from aluminum electrolysis waste slag to turn waste into wealth, both can reduce the discharging of waste residue, can obtain considerable economic simultaneously with realization.
Summary of the invention
The invention provides a kind of method with producing cryolite from aluminum electrolysis waste slag, electrolysis of aluminum waste residue water mill or dry grinding to 60 orders～below 200 orders, behind charcoal in the removal waste residue, the iron, add the vitriol oil, wherein the mass ratio of the vitriol oil and waste residue is 0.5～3: 1, starts to stir, and reacts through 30min～180min under 20 ℃～90 ℃ conditions of temperature, hydrogen fluoride gas water that reaction produces or alkali lye absorb, and alkali lye wherein is soda ash or caustic soda soln.The water that adds 1～20 times of slag quality after reaction finishes, stir 2～20min, again after filtration, add 10%～30% sodium carbonate solution or solid sodium carbonate, 10%～50% hydrofluoric acid in the filtrate, determine the hydrofluoric acid that adds, the amount of yellow soda ash according to the aluminium in the filtrate, sodium content, to satisfy F: Al: Na molecular ratio=6: 1: 3.Under agitation condition, under 20 ℃～95 ℃ conditions, reacted 1～3 hour, obtain cryolite slurry, cryolite slurry is filtered, is washed through disk vacuum filter or whizzer, at drying temperature is under 120 ℃～300 ℃, through air stream drying or rotary kiln drying, gets the sodium aluminum fluoride product.
The present invention can utilize the waste residue that produces in the aluminium electrolysis process, and production cost is low, can recycle after hydrogen fluoride gas process water that produces in the waste residue treating processes or alkali lye absorb and produce the sodium aluminum fluoride product.The method of employing producing cryolite from aluminum electrolysis waste slag provided by the invention both can solve the stacking problem of electrolysis of aluminum waste residue, can turn waste into wealth simultaneously, produced economic benefit.The present invention utilizes the waste residue that produces in the aluminium electrolysis process to produce sodium aluminum fluoride, and production cost is low, can recycle after hydrogen fluoride gas process water that produces in the waste residue treating processes or alkali lye absorb and produce the sodium aluminum fluoride product.
Description of drawings
Fig. 1 is preparation technology's flow process of the present invention.
Embodiment
Example 1:
Get 16kg electrolysis of aluminum waste residue, wet-milling or dry grinding are to 60 orders, after carbon removal and deironing, waste residue is after treatment dropped in the reactor, add vitriol oil 8kg, open and be stirred in 25 ℃ of reaction 160min down, the hydrogen fluoride gas water that reaction produces absorbs, add in the waste residue of 30kg water after acidolysis, stir 2min, filter and remove residue.Filtrate is dropped in the reactor, slowly adds 20% Na under agitation condition
2CO
3Solution 3.5kg and 30% hydrofluoric acid 6kg are 95 ℃ of reaction 1.2h down in temperature of reaction, obtain cryolite slurry, filter and washing through disk vacuum filter, through air stream drying, get sodium aluminum fluoride product 3.4kg under 140 ℃ of conditions.
Embodiment 2
Get 16kg electrolysis of aluminum waste residue, wet-milling or dry grinding are to 150 orders, after carbon removal and deironing, waste residue is after treatment dropped in the reactor, add vitriol oil 12kg, open and be stirred in 60 ℃ of reaction 90min down, the hydrogen fluoride gas NaOH solution absorption that reaction produces, add in the waste residue of 60kg water after acidolysis, stir 5min, filter and remove residue.Filtrate is dropped in the reactor, slowly adds 20% Na under agitation condition
2CO
3Solution 4.2kg and 40% hydrofluoric acid 5.5kg are 80 ℃ of reaction 2h down in temperature of reaction, obtain cryolite slurry, filter and washing through disk vacuum filter, through air stream drying, get sodium aluminum fluoride product 4.0kg under 160 ℃ of conditions.
Embodiment 3
Get 16kg electrolysis of aluminum waste residue, wet-milling or dry grinding after carbon removal and deironing, in waste residue input reactor after treatment, add vitriol oil 15kg to 200 orders, open and be stirred in 80 ℃ of reaction 60min down, react the hydrogen fluoride gas Na that produces
2CO
3Solution absorption adds in the waste residue of 100kg water after acidolysis, stirs 10min, filters and removes residue.Filtrate is dropped in the reactor, slowly adds 20% Na under agitation condition
2CO
3Solution 4.6kg and 40% hydrofluoric acid 6kg are 50 ℃ of reaction 2.5h down in temperature of reaction, obtain cryolite slurry, through whizzer centrifuging and washing, through rotary kiln drying, get sodium aluminum fluoride product 4.4kg under 200 ℃ of conditions.
Embodiment 4
Get 16kg electrolysis of aluminum waste residue, wet-milling or dry grinding are to 200 orders, after carbon removal and deironing, waste residue is after treatment dropped in the reactor, add vitriol oil 25kg, open and be stirred in 80 ℃ of reaction 60min down, the hydrogen fluoride gas water that reaction produces absorbs, add in the waste residue of 150kg water after acidolysis, stir 15min, filter and remove residue.Filtrate is dropped in the reactor, slowly adds solid Na under agitation condition
2CO
31kg and 20% hydrofluoric acid 13kg, reaction 3h obtain cryolite slurry under temperature of reaction is 30 ℃, with whizzer centrifuging and washing, through rotary kiln drying, get sodium aluminum fluoride product 4.6kg under 260 ℃ of conditions.
Claims (3)
1. method with producing cryolite from aluminum electrolysis waste slag, it is characterized in that: electrolysis of aluminum waste residue water mill or dry grinding to 60 orders～below 200 orders, remove the charcoal in the waste residue, behind the iron, add the vitriol oil, start and stir, under 20 ℃～90 ℃ conditions of temperature, react through 30min～180min, hydrogen fluoride gas water that reaction produces or alkali lye absorb, the water that adds 1～20 times of slag quality after reaction finishes, stir 2～20min, more after filtration, add 10%～50% hydrofluoric acid and 10%～30% sodium carbonate solution or solid sodium carbonate in the filtrate, the consumption of the two is according to the aluminium in the filtrate, sodium content is determined, satisfy F: Al: the Na molecular ratio is 6: 1: 3, under agitation condition, reacts 1～3 hour under 20 ℃～95 ℃ conditions, obtain cryolite slurry, cryolite slurry after filtration, washing, get the sodium aluminum fluoride product after the drying.
2. the method with producing cryolite from aluminum electrolysis waste slag as claimed in claim 1 is characterized in that: the treatment agent vitriol oil that the electrolysis of aluminum waste residue behind removal charcoal, the iron is added and the mass ratio of electrolysis of aluminum waste residue are 0.5～3: 1.
3. as claim 1 and described method with producing cryolite from aluminum electrolysis waste slag, it is characterized in that: the alkali lye that hydrogen fluoride gas adopts that absorption reaction produces is caustic soda soln or soda ash solution.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079534A (en) * | 2010-12-16 | 2011-06-01 | 多氟多化工股份有限公司 | Method for producing cryolite by using fluorine-containing waste residues of electrolytic aluminium |
| CN103101948A (en) * | 2011-11-15 | 2013-05-15 | 沈阳铝镁设计研究院有限公司 | Heating method for sulfuric acid leaching of aluminum-containing material |
| CN103950962A (en) * | 2014-05-26 | 2014-07-30 | 河南天辰环保科技股份有限公司 | Process for preparing cryolite by utilizing HF (hydrogen fluoride) waste liquor and prepared cryolite |
| CN105293536A (en) * | 2015-12-01 | 2016-02-03 | 多氟多化工股份有限公司 | Method of extracting lithium from electrolytic aluminium waste residues |
| CN107954410A (en) * | 2017-11-23 | 2018-04-24 | 亚太环保股份有限公司 | A kind of method that electrolyte and charcoal are recycled in the cathode carbon pieces from electrolytic aluminium |
| CN109721090A (en) * | 2019-03-06 | 2019-05-07 | 山东聚科源铝业科技有限公司 | A method of reducing ice crystal molecular proportion |
| CN109972175A (en) * | 2019-04-28 | 2019-07-05 | 沈阳北冶冶金科技有限公司 | A kind of separation and recovery method of the difficult electrolyte of aluminium electroloysis |
-
2008
- 2008-03-11 CN CNB2008100307813A patent/CN100554161C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079534A (en) * | 2010-12-16 | 2011-06-01 | 多氟多化工股份有限公司 | Method for producing cryolite by using fluorine-containing waste residues of electrolytic aluminium |
| CN103101948A (en) * | 2011-11-15 | 2013-05-15 | 沈阳铝镁设计研究院有限公司 | Heating method for sulfuric acid leaching of aluminum-containing material |
| CN103950962A (en) * | 2014-05-26 | 2014-07-30 | 河南天辰环保科技股份有限公司 | Process for preparing cryolite by utilizing HF (hydrogen fluoride) waste liquor and prepared cryolite |
| CN105293536A (en) * | 2015-12-01 | 2016-02-03 | 多氟多化工股份有限公司 | Method of extracting lithium from electrolytic aluminium waste residues |
| CN107954410A (en) * | 2017-11-23 | 2018-04-24 | 亚太环保股份有限公司 | A kind of method that electrolyte and charcoal are recycled in the cathode carbon pieces from electrolytic aluminium |
| CN107954410B (en) * | 2017-11-23 | 2020-04-14 | 亚太环保股份有限公司 | Method for recovering electrolyte and carbon from electrolytic aluminum cathode carbon block |
| CN109721090A (en) * | 2019-03-06 | 2019-05-07 | 山东聚科源铝业科技有限公司 | A method of reducing ice crystal molecular proportion |
| CN109721090B (en) * | 2019-03-06 | 2021-03-23 | 山东绿脉铝业科技有限公司 | Method for reducing cryolite molecular ratio |
| CN109972175A (en) * | 2019-04-28 | 2019-07-05 | 沈阳北冶冶金科技有限公司 | A kind of separation and recovery method of the difficult electrolyte of aluminium electroloysis |
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| CN100554161C (en) | 2009-10-28 |
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Granted publication date: 20091028 Termination date: 20110311 |