CN102992370B - High-purity aluminum fluoride production technology - Google Patents
High-purity aluminum fluoride production technology Download PDFInfo
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- CN102992370B CN102992370B CN201110271803.7A CN201110271803A CN102992370B CN 102992370 B CN102992370 B CN 102992370B CN 201110271803 A CN201110271803 A CN 201110271803A CN 102992370 B CN102992370 B CN 102992370B
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- Prior art keywords
- hydrogen fluoride
- tower
- acid
- sulfuric acid
- aluminum fluoride
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- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 title claims abstract description 49
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005516 engineering process Methods 0.000 title abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 94
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000010436 fluorite Substances 0.000 claims abstract description 20
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 230000008020 evaporation Effects 0.000 claims abstract description 13
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 238000007872 degassing Methods 0.000 claims abstract description 9
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 230000002000 scavenging effect Effects 0.000 claims description 10
- 238000005201 scrubbing Methods 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 239000006200 vaporizer Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to the technical field of aluminum fluoride production, and relates to a production technology of high-purity aluminum fluoride. The technology comprises the steps that: (1) hydrogen fluoride gas desiliconization is carried out, wherein fluorite and sulfuric acid are subjected to a reaction; produced hydrogen fluoride gas sequentially passes through a pre-purification tower and a purification tower, such that sulfuric acid washing and condensation are carried out; condensed acid overflows to a rectification tower through a crude acid tank, and is subjected to desiliconization; degassing is carried out in a degassing tower; and the obtained product overflows to a finished product tank through a rectified acid cooling device; (2) anhydrous hydrogen fluoride evaporation is carried out, wherein the finished product acid is pumped into a hydrogen fluoride distillation tower kettle by using a submerged pump; evaporation is carried out by using an evaporator in the tower kettle; hydrogen fluoride gas after evaporation is delivered through an integral superheater in the tower kettle, and directly flows into a fluidized bed; and (3) aluminum fluoride is produced, wherein the hydrogen fluoride gas enters the fluidized bed and is subjected to a reaction with aluminum hydroxide, such that aluminum fluoride is produced. According to the invention, because anhydrous hydrogen fluoride is adopted as a raw material, and the desiliconization treatment is carried out in the preparation process, the produced aluminum fluoride has the advantages of high purity, low silicon dioxide content, low discretionary reduction amount, and simple and feasible production process.
Description
Technical field
The invention belongs to aluminum fluoride production technical field, relate to a kind of production technique of high-purity aluminum fluoride.
Background technology
Aluminum fluoride is mainly the fusing assistant as electrolytic aluminum, adjusts electrolytical performance, strengthens electroconductibility, reduces electrolysis temperature, is conducive to the electrolysis of aluminum oxide and the energy consumption of reduction electrolytic process.Energy expenditure and the pollutant emission of the Performance and quality of aluminum fluoride directly and in Aluminum Electrolysis Production process is closely bound up.The aluminium fluoride product of high-performance and good quality will make reducing with electric consumption of aluminium electrolysis enterprise, fluorine-containing, sulphur fume emission reduces, the quality product that is more conducive to electrolytic aluminum improves and energy-saving and emission-reduction, is the growth requirement of aluminum electrolysis industry, is also the aluminum fluoride industry developing direction in future.
Along with the domestic and international rapid growth of aluminum fluoride production line quantity in recent years, higher-grade raw material fluorite ore has been on the verge of to adopt sky, the inexorable trend that low-grade fluorite ore deposit and lower taste fluorite ore are aluminum fluoride production industries, yet existing fluorite ore raw material is not up to standard, force the necessary improvement of production process of enterprise, the quality of guarantee product.In fact, SiO in the aluminum fluoride that current conventional dry process is produced
2content usually exceeds standard.
Summary of the invention
The production technique that the object of this invention is to provide a kind of high-purity aluminum fluoride, the aluminum fluoride purity that makes is high, dioxide-containing silica is low, the amount of cutting down according to the circumstance is low, and technique is simply easy to implement.
Described high-purity aluminum fluoride production technique, comprises the steps:
(1) hydrogen fluoride gas desiliconization: fluorite and sulfuric acid reaction generate hydrogen fluoride gas; Hydrogen fluoride gas, through sulfuric acid scrubbing in sulfuric acid scrubbing in preliminary cleaning tower, scavenging tower, enters one-level, secondary coolers; Condensed condensation acid enters thick acid tank, by thick acid tank overflow to rectifying tower, carries out desiliconization, and then enters degassing tower and carry out degassed; Finally enter rectifying acid cooler, by the overflow of rectifying acid cooler to finished product storage tank;
(2) anhydrous hydrogen fluoride evaporation: the finished acid from finished product storage tank is beaten to hydrogen fluoride distillation tower tower reactor by submerged pump, is evaporated by the vaporizer in tower reactor, and the hydrogen fluoride gas after evaporation directly enters fluidized-bed through integral type superheater in tower reactor again;
(3) generate aluminum fluoride: from the hydrogen fluoride gas of superheater, enter fluidized-bed and react generation aluminum fluoride with aluminium hydroxide.
Described fluorite and the mass ratio of sulfuric acid are 1: 2.8, and the concentration of sulfuric acid is 98%.
Described fluorite and the temperature of reaction of sulfuric acid are 515～525 ℃.
In described preliminary cleaning tower and scavenging tower, sulfuric acid is the mixing acid of concentration 98% sulfuric acid and concentration 105% sulfuric acid, and both mixing quality ratios are 3: 1.
Described hydrogen fluoride gas and the temperature of reaction of aluminium hydroxide are 570～590 ℃.
Chemical reaction of the present invention is as follows:
CaF
2+H
2SO
4＝CaSO
4+2HF↑
Main side reaction:
CaF
2in SiO
2the reaction causing:
SiO
2+ 4HF=SiF
4+ 2H
2o (desiliconization)
SiF
4+2HF＝H
2SiF
6
CaF
2in CaCO
3the reaction causing:
CaCO
3+H
2SO
4＝CaSO
4+H
2O+CO
2↑
CaF
2in CaS, MgS, Fe
2o
3, Al
2o
3the reaction causing:
CaS+H
2SO
4＝CaSO
4+H
2S↑
MgS+H
2SO
4＝MgSO
4+H
2S↑
Fe
2O
3+3H
2SO
4＝Fe
2(SO
4)
3+3H
2O
Al
2O
3+3H
2SO
4＝Al
2(SO
4)
3+3H
2O
The reaction being caused by side reaction:
H
2S+H
2SO
4＝S↓+SO
2↑+2H
2O
SO
2+ 2H
2s=3S ↓+2H
2o (degassed)
Desiliconization process: because the boiling point of hydrofluoric acid and silicofluoric acid is different, silicon tetrafluoride is because lower boiling-86 ℃ are first evaporated, and hydrogen fluoride boiling point is relatively high, when reaching 19.54 ℃, stays in rectifying tower, silicon tetrafluoride is taken away by tail gas, finally under the spray of water, is slowly hydrolyzed into silicofluoric acid.
From above-mentioned reaction, the gaseous constituent mainly containing in air guide (gas producing in producing) is HF, CO
2, H
2s and SO
2deng.
Degasification process: the hydrogen sulfide in air guide and sulfur dioxide gas precursor reactant generation elemental sulfur are taken off sulfur dioxide gas and completed degasification process.
Process flow sheet of the present invention is as Fig. 1.
The high-purity aluminum fluoride product performance index making is as following table 1.
The high-purity aluminum fluoride product performance index of table 1 table
Beneficial effect of the present invention is as follows:
The present invention is because raw material adopts anhydrous hydrogen fluoride, and in preparation process, carries out desiliconization processing, and the aluminum fluoride purity that makes is high, dioxide-containing silica is low, the amount of cutting down according to the circumstance is low, and technique is simply easy to implement, specific as follows:
(1) high-purity aluminum fluoride product purity is high, has reduced the aluminum fluoride consumption of ton aluminium;
(2) high-purity aluminium fluoride product is owing to using anhydrous hydrogen fluoride (volume content is more than 99.95%), avoided preferably the hydrolysis reaction in electrolyzer, dioxide-containing silica is extremely low, quality percentage composition is between 0.02～0.04%, improved the quality product of electrolytic aluminum, reduce the energy consumption of electrolytic aluminum, reduced the sulphur pollution discharge of electrolytic aluminum;
(3) high-purity aluminium fluoride product burning decrement (being mainly in conjunction with water) is low, has reduced the fluoride pollution discharge of electrolytic aluminum between 0.3～0.5%.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
A kind of high-purity aluminum fluoride production technique comprises the steps:
(1) hydrogen fluoride gas desiliconization: fluorite and sulfuric acid reaction generate hydrogen fluoride gas; Hydrogen fluoride gas, through sulfuric acid scrubbing in sulfuric acid scrubbing in preliminary cleaning tower, scavenging tower, enters one-level, secondary coolers; Condensed condensation acid enters thick acid tank, by thick acid tank overflow to rectifying tower, carries out desiliconization, and then enters degassing tower and carry out degassed; Finally enter rectifying acid cooler, by the overflow of rectifying acid cooler to finished product storage tank;
(2) anhydrous hydrogen fluoride evaporation: the finished acid from finished product storage tank is beaten to hydrogen fluoride distillation tower tower reactor by submerged pump, is evaporated by the vaporizer in tower reactor, and the hydrogen fluoride gas after evaporation directly enters fluidized-bed through integral type superheater in tower reactor again;
(3) generate aluminum fluoride: from the hydrogen fluoride gas of superheater, enter fluidized-bed and react generation aluminum fluoride with aluminium hydroxide.
Described fluorite and the mass ratio of sulfuric acid are 1: 2.8, and the concentration of sulfuric acid is 98%.
Described fluorite and the temperature of reaction of sulfuric acid are 515 ℃.
In described preliminary cleaning tower and scavenging tower, sulfuric acid is the mixing acid of concentration 98% sulfuric acid and concentration 105% sulfuric acid, and both mixing quality ratios are 3: 1.
Described hydrogen fluoride gas and the temperature of reaction of aluminium hydroxide are 570 ℃.
The high-purity aluminum fluoride product performance index making is as table 2.
High-purity aluminum fluoride product performance index table that table 2 embodiment 1 makes
Embodiment 2
A kind of high-purity aluminum fluoride production technique comprises the steps:
(1) hydrogen fluoride gas desiliconization: fluorite and sulfuric acid reaction generate hydrogen fluoride gas; Hydrogen fluoride gas, through sulfuric acid scrubbing in sulfuric acid scrubbing in preliminary cleaning tower, scavenging tower, enters one-level, secondary coolers; Condensed condensation acid enters thick acid tank, by thick acid tank overflow to rectifying tower, carries out desiliconization, and then enters degassing tower and carry out degassed; Finally enter rectifying acid cooler, by the overflow of rectifying acid cooler to finished product storage tank;
(2) anhydrous hydrogen fluoride evaporation: the finished acid from finished product storage tank is beaten to hydrogen fluoride distillation tower tower reactor by submerged pump, is evaporated by the vaporizer in tower reactor, and the hydrogen fluoride gas after evaporation directly enters fluidized-bed through integral type superheater in tower reactor again;
(3) generate aluminum fluoride: from the hydrogen fluoride gas of superheater, enter fluidized-bed and react generation aluminum fluoride with aluminium hydroxide.
Described fluorite and the mass ratio of sulfuric acid are 1: 2.8, and the concentration of sulfuric acid is 98%.
Described fluorite and the temperature of reaction of sulfuric acid are 520 ℃.
In described preliminary cleaning tower and scavenging tower, sulfuric acid is the mixing acid of concentration 98% sulfuric acid and concentration 105% sulfuric acid, and both mixing quality ratios are 3: 1.
Described hydrogen fluoride gas and the temperature of reaction of aluminium hydroxide are 590 ℃.
The high-purity aluminum fluoride product performance index making is as table 3.
High-purity aluminum fluoride product performance index table that table 3 embodiment 2 makes
Embodiment 3
A kind of high-purity aluminum fluoride production technique comprises the steps:
(1) hydrogen fluoride gas desiliconization: fluorite and sulfuric acid reaction generate hydrogen fluoride gas; Hydrogen fluoride gas, through sulfuric acid scrubbing in sulfuric acid scrubbing in preliminary cleaning tower, scavenging tower, enters one-level, secondary coolers; Condensed condensation acid enters thick acid tank, by thick acid tank overflow to rectifying tower, carries out desiliconization, and then enters degassing tower and carry out degassed; Finally enter rectifying acid cooler, by the overflow of rectifying acid cooler to finished product storage tank;
(2) anhydrous hydrogen fluoride evaporation: the finished acid from finished product storage tank is beaten to hydrogen fluoride distillation tower tower reactor by submerged pump, is evaporated by the vaporizer in tower reactor, and the hydrogen fluoride gas after evaporation directly enters fluidized-bed through integral type superheater in tower reactor again;
(3) generate aluminum fluoride: from the hydrogen fluoride gas of superheater, enter fluidized-bed and react generation aluminum fluoride with aluminium hydroxide.
Described fluorite and the mass ratio of sulfuric acid are 1: 2.8, and the concentration of sulfuric acid is 98%.
Described fluorite and the temperature of reaction of sulfuric acid are 525 ℃.
In described preliminary cleaning tower and scavenging tower, sulfuric acid is the mixing acid of concentration 98% sulfuric acid and concentration 105% sulfuric acid, and both mixing quality ratios are 3: 1.
Described hydrogen fluoride gas and the temperature of reaction of aluminium hydroxide are 580 ℃.
The high-purity aluminum fluoride product performance index making is as table 4.
High-purity aluminum fluoride product performance index table that table 4 embodiment 3 makes
Claims (1)
1. a production technique for high-purity aluminum fluoride, is characterized in that comprising the steps:
(1) hydrogen fluoride gas desiliconization: fluorite and sulfuric acid reaction generate hydrogen fluoride gas; Hydrogen fluoride gas, through sulfuric acid scrubbing in sulfuric acid scrubbing in preliminary cleaning tower, scavenging tower, enters one-level, secondary coolers; Condensed condensation acid enters thick acid tank, by thick acid tank overflow to rectifying tower, carries out desiliconization, and then enters degassing tower and carry out degassed; Finally enter rectifying acid cooler, by the overflow of rectifying acid cooler to finished product storage tank;
Described fluorite and the mass ratio of sulfuric acid are 1:2.8, and the concentration of sulfuric acid is 98%;
Described fluorite and the temperature of reaction of sulfuric acid are 515 ~ 525 ℃;
In described preliminary cleaning tower and scavenging tower, sulfuric acid is the mixing acid of concentration 98% sulfuric acid and concentration 105% sulfuric acid, and both mixing qualities are than being 3:1;
(2) anhydrous hydrogen fluoride evaporation: the finished acid from finished product storage tank is beaten to hydrogen fluoride distillation tower tower reactor by submerged pump, is evaporated by the vaporizer in tower reactor, and the hydrogen fluoride gas after evaporation directly enters fluidized-bed through integral type superheater in tower reactor again;
(3) generate aluminum fluoride: from the hydrogen fluoride gas of superheater, enter fluidized-bed and react generation aluminum fluoride with aluminium hydroxide; Described hydrogen fluoride gas and the temperature of reaction of aluminium hydroxide are 570 ~ 590 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110271803.7A CN102992370B (en) | 2011-09-14 | 2011-09-14 | High-purity aluminum fluoride production technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110271803.7A CN102992370B (en) | 2011-09-14 | 2011-09-14 | High-purity aluminum fluoride production technology |
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| Publication Number | Publication Date |
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| CN102992370A CN102992370A (en) | 2013-03-27 |
| CN102992370B true CN102992370B (en) | 2014-09-10 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732117A (en) * | 2020-06-19 | 2020-10-02 | 锦洋高新材料股份有限公司 | Method for preparing anhydrous aluminum fluoride by purification and evaporation integration |
| CN111661860A (en) * | 2020-06-19 | 2020-09-15 | 锦洋高新材料股份有限公司 | Production method of anhydrous aluminum fluoride |
| CN111943244A (en) * | 2020-08-12 | 2020-11-17 | 山东昭和新材料科技股份有限公司 | Method for producing low-silicon dry-process aluminum fluoride by using high-silicon fluorite powder |
| CN111874932A (en) * | 2020-08-12 | 2020-11-03 | 山东昭和新材料科技股份有限公司 | Method for controlling phosphorus content in aluminum fluoride production |
| CN111960452A (en) * | 2020-08-27 | 2020-11-20 | 北京理工大学 | Preparation method of aluminum fluoride powder |
| CN112777621A (en) * | 2020-12-30 | 2021-05-11 | 淄博华士元环保科技有限公司 | Method for preparing aluminum fluoride by recycling fluorine-containing waste |
| CN115869864B (en) * | 2022-12-27 | 2024-06-25 | 兰州理工大学 | Production system and method of anhydrous aluminum fluoride |
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|---|---|---|---|---|
| CN101077789A (en) * | 2006-05-22 | 2007-11-28 | 多氟多化工股份有限公司 | Method for preparing aluminum fluoride |
| CN101134592A (en) * | 2006-09-01 | 2008-03-05 | 多氟多化工股份有限公司 | Preparation method of aluminun fluoride |
| CN101139106A (en) * | 2007-08-25 | 2008-03-12 | 宁夏金和化工有限公司 | Desilication method in the dry type naluminum fluoride production |
| CN101264915A (en) * | 2008-04-21 | 2008-09-17 | 河南未来铝业（集团）有限公司 | Technique for producing aluminum fluoride by dry method |
-
2011
- 2011-09-14 CN CN201110271803.7A patent/CN102992370B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077789A (en) * | 2006-05-22 | 2007-11-28 | 多氟多化工股份有限公司 | Method for preparing aluminum fluoride |
| CN101134592A (en) * | 2006-09-01 | 2008-03-05 | 多氟多化工股份有限公司 | Preparation method of aluminun fluoride |
| CN101139106A (en) * | 2007-08-25 | 2008-03-12 | 宁夏金和化工有限公司 | Desilication method in the dry type naluminum fluoride production |
| CN101264915A (en) * | 2008-04-21 | 2008-09-17 | 河南未来铝业（集团）有限公司 | Technique for producing aluminum fluoride by dry method |
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