CN102219249A - Production method of cryolite - Google Patents
Production method of cryolite Download PDFInfo
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- CN102219249A CN102219249A CN 201110124005 CN201110124005A CN102219249A CN 102219249 A CN102219249 A CN 102219249A CN 201110124005 CN201110124005 CN 201110124005 CN 201110124005 A CN201110124005 A CN 201110124005A CN 102219249 A CN102219249 A CN 102219249A
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Abstract
The invention discloses a production method of cryolite. With electrolytic aluminium fluorine-containing waste residues from flotation and single cryolite which is the byproduct of polysilicon material production as the raw material, and the method comprises the steps of: weighing the electrolytic aluminium fluorine-containing waste residues from flotation and the single cryolite as the byproduct of polysilicon material production; mixing the weighed electrolytic aluminium fluorine-containing waste residues from flotation and the single cryolite as a byproduct of polysilicon material production with a fluorine containing hydrochloric acid solution, then leaving the mixture reacting for 1-6 hours under stirring DEG C, filtering the mixture, washing a filter cake with water and drying the filter cake, thus obtaining the cryolite product. And the generated filtrate and washing liquid can be treated with lime so as to be discharged or used in calcium chloride production. By combining the current development situation of fluorine chemical industry, the invention makes fully use of low grade fluorine resources and makes the recycling of fluorine resources come true. In addition, the invention also provides a solution to the waste treatment problem that restricts the development of the fluorine chemical industry.
Description
Technical field
The present invention relates to chemical production technical field, be specifically related to a kind of method of utilizing the fluorine-containing waste production sodium aluminum fluoride that produces in the fluorochemical application process.
Background technology
The natural cryolite ore reserves seldom, at present the sodium aluminum fluoride that uses mostly is a synthetic.The sodium aluminum fluoride production technique mainly contains clay bittern method, hydrofluoaluminic acid soda ash method, Sodium Silicofluoride method and hydrofluoric acid, sodium aluminate method etc.The fluorine source of producing at present sodium aluminum fluoride is mainly fluorite, and fluorite is as a kind of grand strategy resource that develops nuclear industry, and standing stock are limited, and each state all pays much attention to the protection to fluorite resource, even takes the policy of a large amount of import fluorites to lay in.China's fluorite resource reserves rank first in the world, and as non-renewable grand strategy resource, China began to limit issuing of fluorite mining card in 2003, the limit licensing system is carried out in outlet, make fluorite price increase and buying difficulty.Along with the scarcity day by day of fluorite resource in the world wide, causing the inorganic fluorine chemical industry to seek other fluorine resources becomes inexorable trend.Actively seek new fluorine resource, encouraging the utilization of fluorine resource circulation is the industry policy that country supports energetically.
Sodium aluminum fluoride is mainly used in the solubility promoter of metal smelting aluminium, also can be used as the opalizer and the solubility promoter of sterilant, enamel opacifier, glass and the enamel production usefulness of farm crop.Electrolytic aluminum is as the user of sodium aluminum fluoride maximum, it can produce a large amount of fluorine-containing waste residue in process of production, contain 30% sodium aluminum fluoride, 1% aluminum oxide, 1% calcium oxide in this fluorine-containing waste residue approximately, all the other are impurity such as carbon granule, carbon element of graphite, aluminium carbide and ferrosilicon oxide compound.Too high because of its foreign matter content, all be the method that adopts heap to abandon in the past, owing to contain 30% sodium aluminum fluoride in the fluorine-containing waste residue, sodium aluminum fluoride contains 55% fluorine, therefore both environment is polluted, and a large amount of fluorine is wasted.Adopt flotation to recycle for this part fluorine-containing waste residue at present, but because the restriction of floatation equipment and separating device, the sodium aluminum fluoride content that floatingly selects is low, the foreign matter content height, especially fluorine content is on the low side, and silicon, iron level are higher, can not reach the requirement of the required sodium aluminum fluoride of electrolytic aluminum.
In addition, along with the exhaustion of fossil energy, substitute energys such as development and use wind-force, photovoltaic, underground heat are imperative.And crystalline silicon material (comprising polysilicon and silicon single crystal) is topmost photovoltaic material, and its share of market is more than 90%, and also still be the main flow material of solar cell one quite long from now on period.Production of polysilicon technology comprises multiple synthesis techniques such as improvement Siemens Method, magnesium silicide method, REC method, silane thermal decomposition process at present.Comparatively speaking, inorganic producing and manufacturing technique such as silane thermal decomposition process has starting material and is easy to get, and energy consumption is low, cost is low, and the characteristics that environmental protection pressure is little are directions of following polysilicon development.But 1 ton of polysilicon of the every production of inorganic silane method will produce 4.5 tons of single sodium aluminum fluorides that foreign matter content is higher at least, its main component is tetrafluoro sodium aluminate, aluminium simple substance, silicon-containing compound etc., because of its complicated component, the processing costs height is so the general now mode that adopts stacking or bury is handled.This had both caused environmental pollution, caused the wasting of resources again, was the bottleneck of restriction photovoltaic industry development.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the fluorine-containing waste production sodium aluminum fluoride that produces in the fluorochemical application process.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of production method of sodium aluminum fluoride is raw material with the electrolytic aluminium containing waste slag of fluorine after the flotation with single sodium aluminum fluoride of producing the polycrystalline silicon material by-product, may further comprise the steps:
(1) take by weighing the electrolytic aluminium containing waste slag of fluorine after the flotation and produce single sodium aluminum fluoride of polycrystalline silicon material by-product, the electrolytic aluminium containing waste slag of fluorine after the flotation with the weight proportion of single sodium aluminum fluoride of producing the polycrystalline silicon material by-product is: the electrolytic aluminium containing waste slag of fluorine after the flotation: single sodium aluminum fluoride=(1.0～2.0) that produce the polycrystalline silicon material by-product: 1;
(2) with the electrolytic aluminium containing waste slag of fluorine after the flotation that takes by weighing, single sodium aluminum fluoride of producing the polycrystalline silicon material by-product mixes with fluorine-containing hydrochloric acid soln, the weight of fluorine-containing hydrochloric acid soln is 1～15 times of gross weight of the electrolytic aluminium containing waste slag of fluorine after the flotation and single sodium aluminum fluoride of producing the polycrystalline silicon material by-product, afterwards 20～90 ℃ of following stirring reactions 1～6 hour, filter then, wash filter cake with water, the filter cake drying promptly gets the sodium aluminum fluoride product, the weight percent content of fluorine is 52～55% in this sodium aluminum fluoride product, gained filtrate and washings with lime treatment after discharging or be used to produce calcium chloride.
Further, the weight percent content of Al is 14～19% in the electrolytic aluminium containing waste slag of fluorine after the described flotation, and the weight percent content of Na is 20～24%, SiO
2Weight percent content be 0～5%, Fe
2O
3Weight percent content be 0～3%, the weight percent content of F is 40～50%.
The weight percent content of Al is 15～25% in single sodium aluminum fluoride of described production polycrystalline silicon material by-product, and the weight percent content of Na is 0～24%, SiO
2Weight percent content be 0～1.5%, the weight percent content of F is 54～70%.
Described fluorine-containing hydrochloric acid soln is the mother liquor of acid system ice making spar by-product.The weight percent content of HCl is 1～15% in the described fluorine-containing hydrochloric acid soln, and the content of F is 2～10g/l.
The present invention has made full use of low-grade fluorine resource in conjunction with the present situation of fluorine chemical industry development, has realized the utilization of fluorine resource circulation, and has solved the handling problem of the waste of restriction fluorine chemical industry development.
The production method of sodium aluminum fluoride provided by the invention has following advantage: 1) electrolytic aluminium containing waste slag of fluorine after the flotation and single sodium aluminum fluoride of producing the polycrystalline silicon material by-product are developed as the high-quality sodium aluminum fluoride, have avoided the waste of environmental pollution and a large amount of fluorine resource; 2) fluorine-containing waste recycle in the fluorochemical application process, make fluorine chemical industry fluorine resource obtain recycle on the one hand, the existing fluorine resource of protection, reduce fluorine chemical industry production cost, solve the bottleneck of the downstream industry development of restriction fluorine chemical application on the other hand, impelled the healthy fast development of downstream industry; 3) handle fluorine-containing waste residue with the fluorine-containing hydrochloric acid soln of mother liquor of acid system ice making spar by-product, realized waste liquid recycling, the fluorine in the waste liquid is further recycled; 4) the sodium aluminum fluoride quality product that is generated reaches the GB requirement, can satisfy the service requirements of Aluminium Electrolysis; 5) raw material of the inventive method employing all is the fluorochemical waste, has alleviated the environmental protection pressure in existing fluorochemical production and the application process on the one hand, and the inventive method can not produce secondary pollution on the other hand, has really realized being worth promoting cleaner production.
Embodiment
Embodiment 1
The production method of present embodiment sodium aluminum fluoride is raw material with the electrolytic aluminium containing waste slag of fluorine after the flotation with single sodium aluminum fluoride of producing the polycrystalline silicon material by-product, may further comprise the steps:
(1) takes by weighing single sodium aluminum fluoride that electrolytic aluminium containing waste slag of fluorine after the 100g flotation and 60g produce the polycrystalline silicon material by-product;
(2) single sodium aluminum fluoride of the electrolytic aluminium containing waste slag of fluorine after the flotation that step (1) is taken by weighing, production polycrystalline silicon material by-product mixes with the fluorine-containing hydrochloric acid soln of 1500g, afterwards 90 ℃ of following stirring reactions 1 hour, filter then, wash filter cake with water, the filter cake drying promptly gets the sodium aluminum fluoride product, the weight percent content of fluorine is 52% in this sodium aluminum fluoride product, and gained filtrate and washings discharge after with lime treatment.
Wherein the weight percent content of Al is 14% in the electrolytic aluminium containing waste slag of fluorine after the flotation, and the weight percent content of Na is 24%, SiO
2Weight percent content be 5%, Fe
2O
3Weight percent content be 3%, the weight percent content of F is 40%.The weight percent content of Al is 15% in single sodium aluminum fluoride of production polycrystalline silicon material by-product, and the weight percent content of Na is 24%, SiO
2Weight percent content be 1.5%, the weight percent content of F is 54%.Fluorine-containing hydrochloric acid soln is the mother liquor of acid system ice making spar by-product, and wherein the weight percent content of HCl is 15%, and the content of F is 2g/l.
Embodiment 2
The production method of present embodiment sodium aluminum fluoride is raw material with the electrolytic aluminium containing waste slag of fluorine after the flotation with single sodium aluminum fluoride of producing the polycrystalline silicon material by-product, may further comprise the steps:
(1) takes by weighing single sodium aluminum fluoride that electrolytic aluminium containing waste slag of fluorine after the 100g flotation and 100g produce the polycrystalline silicon material by-product;
(2) single sodium aluminum fluoride of the electrolytic aluminium containing waste slag of fluorine after the flotation that step (1) is taken by weighing, production polycrystalline silicon material by-product mixes with the fluorine-containing hydrochloric acid soln of 200g, afterwards 20 ℃ of following stirring reactions 6 hours, filter then, wash filter cake with water, the filter cake drying promptly gets the sodium aluminum fluoride product, the weight percent content of fluorine is 53.2% in this sodium aluminum fluoride product, and gained filtrate and washings are used to produce calcium chloride after with lime treatment.
Wherein the weight percent content of Al is 19% in the electrolytic aluminium containing waste slag of fluorine after the flotation, and the weight percent content of Na is 20%, SiO
2Weight percent content be 1%, Fe
2O
3Weight percent content be 2%, the weight percent content of F is 50%.The weight percent content of Al is 25% in single sodium aluminum fluoride of production polycrystalline silicon material by-product, and the weight percent content of Na is 4%, SiO
2Weight percent content be 1%, the weight percent content of F is 70%.Fluorine-containing hydrochloric acid soln is the mother liquor of acid system ice making spar by-product, and wherein the weight percent content of HCl is 1%, and the content of F is 2g/l.
Embodiment 3
The production method of present embodiment sodium aluminum fluoride is raw material with the electrolytic aluminium containing waste slag of fluorine after the flotation with single sodium aluminum fluoride of producing the polycrystalline silicon material by-product, may further comprise the steps:
(1) takes by weighing single sodium aluminum fluoride that electrolytic aluminium containing waste slag of fluorine after the 100g flotation and 50g produce the polycrystalline silicon material by-product;
(2) single sodium aluminum fluoride of the electrolytic aluminium containing waste slag of fluorine after the flotation that step (1) is taken by weighing, production polycrystalline silicon material by-product mixes with the fluorine-containing hydrochloric acid soln of 2250g, afterwards 50 ℃ of following stirring reactions 2 hours, filter then, wash filter cake with water, the filter cake drying promptly gets the sodium aluminum fluoride product, the weight percent content of fluorine is 55% in this sodium aluminum fluoride product, and gained filtrate and washings are used to produce calcium chloride after with lime treatment.
Wherein the weight percent content of Al is 16% in the electrolytic aluminium containing waste slag of fluorine after the flotation, and the weight percent content of Na is 22%, SiO
2Weight percent content be 3%, Fe
2O
3Weight percent content be 1.8%, the weight percent content of F is 41%.The weight percent content of Al is 17% in single sodium aluminum fluoride of production polycrystalline silicon material by-product, and the weight percent content of Na is 13%, SiO
2Weight percent content be 0.5%, the weight percent content of F is 63%.Fluorine-containing hydrochloric acid soln is the mother liquor of acid system ice making spar by-product, and wherein the weight percent content of HCl is 9%, and the content of F is 10g/l.
The sodium aluminum fluoride product that embodiment 1-embodiment 3 is made has carried out mass analysis, and analytical results is shown in Table 1.From the analytical results of table 1 as can be seen, the sodium aluminum fluoride quality product that each embodiment generated all reaches GB, can satisfy the service requirements of Aluminium Electrolysis.
The mass analysis result of each embodiment sodium aluminum fluoride product of table 1
Claims (5)
1. the production method of a sodium aluminum fluoride is characterized in that, is raw material with the electrolytic aluminium containing waste slag of fluorine after the flotation with single sodium aluminum fluoride of producing the polycrystalline silicon material by-product, may further comprise the steps:
(1) take by weighing the electrolytic aluminium containing waste slag of fluorine after the flotation and produce single sodium aluminum fluoride of polycrystalline silicon material by-product, the electrolytic aluminium containing waste slag of fluorine after the flotation with the weight proportion of single sodium aluminum fluoride of producing the polycrystalline silicon material by-product is: the electrolytic aluminium containing waste slag of fluorine after the flotation: single sodium aluminum fluoride=(1.0～2.0) that produce the polycrystalline silicon material by-product: 1;
(2) with the electrolytic aluminium containing waste slag of fluorine after the flotation that takes by weighing, single sodium aluminum fluoride of producing the polycrystalline silicon material by-product mixes with fluorine-containing hydrochloric acid soln, the weight of fluorine-containing hydrochloric acid soln is 1～15 times of gross weight of the electrolytic aluminium containing waste slag of fluorine after the flotation and single sodium aluminum fluoride of producing the polycrystalline silicon material by-product, afterwards 20～90 ℃ of following stirring reactions 1～6 hour, filter then, wash filter cake with water, the filter cake drying promptly gets the sodium aluminum fluoride product, the weight percent content of fluorine is 52～55% in this sodium aluminum fluoride product, gained filtrate and washings with lime treatment after discharging or be used to produce calcium chloride.
2. the production method of sodium aluminum fluoride according to claim 1 is characterized in that, the weight percent content of Al is 14～19% in the electrolytic aluminium containing waste slag of fluorine after the described flotation, and the weight percent content of Na is 20～24%, SiO
2Weight percent content be 0～5%, Fe
2O
3Weight percent content be 0～3%, the weight percent content of F is 40～50%.
3. the production method of sodium aluminum fluoride according to claim 1 is characterized in that, the weight percent content of Al is 15～25% in single sodium aluminum fluoride of described production polycrystalline silicon material by-product, and the weight percent content of Na is 0～24%, SiO
2Weight percent content be 0～1.5%, the weight percent content of F is 54～70%.
4. the production method of sodium aluminum fluoride according to claim 1 is characterized in that, described fluorine-containing hydrochloric acid soln is the mother liquor of acid system ice making spar by-product.
5. the production method of sodium aluminum fluoride according to claim 4 is characterized in that, the weight percent content of HCl is 1～15% in the described fluorine-containing hydrochloric acid soln, and the content of F is 2～10g/l.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110124005 CN102219249A (en) | 2011-05-14 | 2011-05-14 | Production method of cryolite |
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| CN 201110124005 CN102219249A (en) | 2011-05-14 | 2011-05-14 | Production method of cryolite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718244A (en) * | 2012-07-13 | 2012-10-10 | 六九硅业有限公司 | Preparation method of cryolite |
| CN105502453A (en) * | 2016-01-14 | 2016-04-20 | 焦作金凯源铝业有限公司 | Production process for conducting flotation and drying on regenerative cryolite |
| CN109775740A (en) * | 2019-03-22 | 2019-05-21 | 焦作市增氟科技有限公司 | A kind of processing method of by-product list ice crystal when producing organosilicon |
Citations (4)
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|---|---|---|---|---|
| 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 |
| US3493330A (en) * | 1966-11-22 | 1970-02-03 | Reynolds Metals Co | Beneficiation of cryolite material |
| CN101376518A (en) * | 2007-08-30 | 2009-03-04 | 多氟多化工股份有限公司 | Process for preparing kryocide |
| CN101531386A (en) * | 2009-03-03 | 2009-09-16 | 多氟多化工股份有限公司 | Method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid |
-
2011
- 2011-05-14 CN CN 201110124005 patent/CN102219249A/en active Pending
Patent Citations (4)
| 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 |
| US3493330A (en) * | 1966-11-22 | 1970-02-03 | Reynolds Metals Co | Beneficiation of cryolite material |
| CN101376518A (en) * | 2007-08-30 | 2009-03-04 | 多氟多化工股份有限公司 | Process for preparing kryocide |
| CN101531386A (en) * | 2009-03-03 | 2009-09-16 | 多氟多化工股份有限公司 | Method for recovering cryolite from waste slag of electrolytic aluminium by fluorine-containing hydrochloric acid |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718244A (en) * | 2012-07-13 | 2012-10-10 | 六九硅业有限公司 | Preparation method of cryolite |
| CN105502453A (en) * | 2016-01-14 | 2016-04-20 | 焦作金凯源铝业有限公司 | Production process for conducting flotation and drying on regenerative cryolite |
| CN105502453B (en) * | 2016-01-14 | 2017-01-25 | 李国法 | Production process for conducting flotation and drying on regenerative cryolite |
| CN109775740A (en) * | 2019-03-22 | 2019-05-21 | 焦作市增氟科技有限公司 | A kind of processing method of by-product list ice crystal when producing organosilicon |
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Application publication date: 20111019 |