EP0455590B1 - Regulierung und Stabilisierung des A1F3-Gehaltes in einer Aluminiumelektrolysezelle - Google Patents
Regulierung und Stabilisierung des A1F3-Gehaltes in einer Aluminiumelektrolysezelle Download PDFInfo
- Publication number
- EP0455590B1 EP0455590B1 EP91810305A EP91810305A EP0455590B1 EP 0455590 B1 EP0455590 B1 EP 0455590B1 EP 91810305 A EP91810305 A EP 91810305A EP 91810305 A EP91810305 A EP 91810305A EP 0455590 B1 EP0455590 B1 EP 0455590B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alf3
- days
- content
- addition
- time delay
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 16
- 238000005868 electrolysis reaction Methods 0.000 title claims description 15
- 239000004411 aluminium Substances 0.000 title claims description 6
- 230000001105 regulatory effect Effects 0.000 title claims description 3
- 230000000087 stabilizing effect Effects 0.000 title description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 172
- 238000007792 addition Methods 0.000 claims description 30
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- 235000013024 sodium fluoride Nutrition 0.000 claims description 11
- 239000011775 sodium fluoride Substances 0.000 claims description 11
- 238000012821 model calculation Methods 0.000 claims description 10
- 230000004907 flux Effects 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 230000001934 delay Effects 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 230000003019 stabilising effect Effects 0.000 claims 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 16
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- 239000000654 additive Substances 0.000 description 5
- 229910001610 cryolite Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000729 antidote Substances 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- -1 sodium aluminum fluorine Chemical compound 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/20—Automatic control or regulation of cells
Definitions
- the invention relates to a method for regulating and stabilizing an AlF3 content of at least 10% by weight in the bath of an electrolysis cell for the production of aluminum from aluminum oxide dissolved in a cryolite melt.
- a bath or an electrolyte which essentially consists of cryolite, a sodium aluminum fluorine compound (3NaF.AlF3).
- This cryolite in addition to the aluminum oxide to be dissolved, in particular also has substances which lower the melting point, for example aluminum trifluoride AlF3, lithium fluoride LiF, calcium difluoride CaF2 and / or magnesium difluoride MgF2.
- a bath in an electrolysis cell for the production of aluminum contains 6 to 8% by weight of AlF3, 4 to 6% by weight of CaF2, 1 to 2% by weight of LiF, the rest being cryolite.
- the melting point of the bath is lowered in the range of 940 to 970 ° C, the industrial temperature range.
- bath additives do not only have positive effects, e.g. a lowering of the melting point, but often also have a negative effect.
- the addition of lithium fluoride, for example, does not allow film qualities for capacitors without special metal treatment.
- the inventor has set itself the task of creating a method of the type mentioned, with which the fluctuations in the AlF3 content and thus the bath temperature can be brought to a small standard deviation even without lithium fluoride additives, for the AlF3 content to about 1 up to 2%.
- Counteractive additives with neutralizing Effects, such as soda or sodium fluoride, should not be used or should only be used in exceptional cases.
- AlF3 During aluminum electrolysis there is always a loss of AlF3, on the one hand by evaporation, which does not affect the environment or only to a very small extent in encapsulated aluminum electrolysis cells, and on the other hand by reaction with Na2O contained in the added alumina.
- AlF3 there are tables listing the units to be added depending on the bath temperature and the AlF3 content to be set. These tables can be refined by using general correction factors such as Cell age, number of anode effects, trend of concentration are taken into account.
- the measurement and analysis of the individual state of aluminum electrolysis and the determination of the optimal time shift are not only carried out separately for each cell, but also at different intervals, if need be. In the case of healthy, normally working cells, this is preferably done every 1 to 2 months, in the case of poor oven operation, repeated 1 to 5 days apart from the program until the oven operation improves and the intervals can be extended again. Thanks to the individual, up-to-date recording of the cell status, general Tables that do not take into account either the cell type or its condition are omitted.
- the measurement of the AlF3 content can be replaced by a temperature measurement. This is not only easier, but inevitably records a temperature dependency of the AlF3 content and can be used directly.
- the most important parameters for the model calculation used according to the invention are the flux mass M and the daily AlF3 losses v. These parameters are calculated from measurements of the concentration c and the additions z of AlF3 in the electrolyte over a period t1 of preferably 10 to 60 days, in particular 20 to 30 days.
- the period t 1 is so short on the one hand that the individual condition of a cell can currently be recorded, but on the other hand so long that random, short-term changes without a trend are not taken into account.
- the calculated flux mass M and daily AlF3 losses v are included in the model calculation and calculated with time shifts ZV of preferably 1 to 10 whole days.
- the best parameter set is selected in accordance with known statistical criteria and the addition z of AlF3 is calculated by specifying an AlF3 content c of between 10 and 15% by weight.
- the specification for the AlF3 content c depends on the electrolysis temperature which is considered optimal. This can be obtained, for example, with about 12% by weight aluminum fluoride.
- the best parameter set containing the time shift ZV is used for the addition of z of aluminum fluoride for the next n days.
- M the flux mass
- c s the target value for the AlF3 content
- c m the instantaneous value for the AlF3 content
- v the daily AlF3 loss.
- the period of n days should generally not be greater than the period t 1 during which the basics for determining the parameters were measured.
- the time period is corrected by the time difference ZV.
- a modified formula can be used to predict how high the aluminum fluoride content c x should be on the day t x according to the model calculation.
- the model can be checked for suitability by a measurement on the relevant day t x and adjusted if necessary.
- intraday values can also be used to determine the optimal time shift ZV for the AlF3 addition z can be entered. Since the optimal time shift ZV determined for the addition of aluminum fluoride for electrolysis cells used in the aluminum industry is generally in the range from 2 to 5 days, in particular 3 days, according to a further developed embodiment of the invention, intraday time shifts ZV are calculated in this period and listed to determine the best parameter set. The rough grid for the time shift ZV can be brought down to the fineness required in practice by the introduction of a decimal place.
- the aluminum fluoride is conventionally introduced in bags, more modern cells work with dosing devices, and increasingly the dense phase conveyance is used.
- the metering devices or devices are preferably controlled by a process computer and release the aluminum fluoride in portions or continuously.
- the fluctuations in the AlF3 concentration in the electrolyte can be reduced to a standard deviation of 1 to 2%, which in a concentration range of 10 to 15% by weight of aluminum fluoride leads to simplified process control and a well-known increase in the production of aluminum. Excessive target values can be prevented, as can the addition of an antidote such as soda or sodium fluoride. Electrolyte additives, such as lithium fluoride, which have a detrimental effect in certain uses, are not necessary.
- Fig. 1 the typical time course of the AlF3 concentration (wt .-%) with the corresponding AlF3 additions in kg / day is given. You can see the strong fluctuations between 5 and 15% of the AlF3 excess, caused by the delayed reaction of the electrolytic cell to the AlF3 addition.
- Table II shows the calculation of the optimal addition for stabilizing the AlF3 concentration.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1527/90 | 1990-05-04 | ||
| CH152790 | 1990-05-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0455590A1 EP0455590A1 (de) | 1991-11-06 |
| EP0455590B1 true EP0455590B1 (de) | 1995-06-28 |
Family
ID=4212527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91810305A Expired - Lifetime EP0455590B1 (de) | 1990-05-04 | 1991-04-24 | Regulierung und Stabilisierung des A1F3-Gehaltes in einer Aluminiumelektrolysezelle |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5094728A (is) |
| EP (1) | EP0455590B1 (is) |
| AU (1) | AU643006B2 (is) |
| CA (1) | CA2041440A1 (is) |
| DE (1) | DE59105830D1 (is) |
| ES (1) | ES2075401T3 (is) |
| IS (1) | IS1632B (is) |
| NO (1) | NO304748B1 (is) |
| ZA (1) | ZA913260B (is) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19805619C2 (de) * | 1998-02-12 | 2002-08-01 | Heraeus Electro Nite Int | Verfahren zur Regelung des AlF¶3¶-Gehaltes in Kryolithschmelzen |
| FR2821364B1 (fr) * | 2001-02-28 | 2004-04-09 | Pechiney Aluminium | Procede de regulation d'une cellule d'electrolyse |
| FR2821363B1 (fr) * | 2001-02-28 | 2003-04-25 | Pechiney Aluminium | Procede de regulation d'une cellule d'electrolyse |
| EP1344847A1 (de) * | 2001-12-03 | 2003-09-17 | Alcan Technology & Management AG | Regulierung einer Aluminiumelektrolysezelle |
| US9771659B2 (en) * | 2013-03-13 | 2017-09-26 | Alcoa Usa Corp. | Systems and methods of protecting electrolysis cell sidewalls |
| CN104451779B (zh) * | 2014-12-17 | 2017-01-18 | 湖南创元铝业有限公司 | 铝电解槽氟化铝控制方法 |
| WO2020190271A1 (en) * | 2019-03-16 | 2020-09-24 | General Electric Company | System and method for controlling of smelting pot line |
| CN117210879B (zh) * | 2023-10-12 | 2025-02-11 | 中国铝业股份有限公司 | 一种铝电解槽用氟化铝添加量计算方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3380897A (en) * | 1964-11-16 | 1968-04-30 | Reynolds Metals Co | Method of determining ore concentration |
| US3471390A (en) * | 1965-03-24 | 1969-10-07 | Reynolds Metals Co | Alumina concentration meter |
| NO166821C (no) * | 1985-02-21 | 1991-09-04 | Aardal & Sunndal Verk As | Fremgangsmaate for styring av aluminiumoksyd-tilfoerselen til elektrolyseovner for fremstilling av aluminium. |
| DE3564825D1 (en) * | 1985-03-18 | 1988-10-13 | Alcan Int Ltd | Controlling alf 3 addition to al reduction cell electrolyte |
| FR2581660B1 (fr) * | 1985-05-07 | 1987-06-05 | Pechiney Aluminium | Procede de regulation precise d'une faible teneur en alumine dans une cuve d'electrolyse ignee pour la production d'aluminium |
| US4654130A (en) * | 1986-05-15 | 1987-03-31 | Reynolds Metals Company | Method for improved alumina control in aluminum electrolytic cells employing point feeders |
| US4814050A (en) * | 1986-10-06 | 1989-03-21 | Aluminum Company Of America | Estimation and control of alumina concentration in hall cells |
| FR2620738B1 (fr) * | 1987-09-18 | 1989-11-24 | Pechiney Aluminium | Procede de regulation de l'acidite du bain d'electrolyse par recyclage des produits fluores emis par les cuves d'electrolyse hall-heroult |
-
1991
- 1991-04-24 EP EP91810305A patent/EP0455590B1/de not_active Expired - Lifetime
- 1991-04-24 DE DE59105830T patent/DE59105830D1/de not_active Expired - Fee Related
- 1991-04-24 ES ES91810305T patent/ES2075401T3/es not_active Expired - Lifetime
- 1991-04-29 AU AU76015/91A patent/AU643006B2/en not_active Ceased
- 1991-04-29 CA CA002041440A patent/CA2041440A1/en not_active Abandoned
- 1991-04-29 US US07/693,939 patent/US5094728A/en not_active Expired - Fee Related
- 1991-04-30 ZA ZA913260A patent/ZA913260B/xx unknown
- 1991-04-30 NO NO911708A patent/NO304748B1/no not_active IP Right Cessation
- 1991-05-02 IS IS3698A patent/IS1632B/is unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IS1632B (is) | 1996-07-19 |
| NO911708D0 (no) | 1991-04-30 |
| AU643006B2 (en) | 1993-11-04 |
| CA2041440A1 (en) | 1991-11-05 |
| DE59105830D1 (de) | 1995-08-03 |
| NO911708L (no) | 1991-11-05 |
| ES2075401T3 (es) | 1995-10-01 |
| ZA913260B (en) | 1992-01-29 |
| NO304748B1 (no) | 1999-02-08 |
| US5094728A (en) | 1992-03-10 |
| EP0455590A1 (de) | 1991-11-06 |
| AU7601591A (en) | 1991-11-07 |
| IS3698A7 (is) | 1991-11-05 |
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