CN108118366A - A kind of method of alumina dissolution speed in quickening aluminium cell - Google Patents
A kind of method of alumina dissolution speed in quickening aluminium cell Download PDFInfo
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- CN108118366A CN108118366A CN201810006567.8A CN201810006567A CN108118366A CN 108118366 A CN108118366 A CN 108118366A CN 201810006567 A CN201810006567 A CN 201810006567A CN 108118366 A CN108118366 A CN 108118366A
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- alf
- aluminium
- electrolyte
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 52
- 239000004411 aluminium Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 27
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004090 dissolution Methods 0.000 title claims abstract description 14
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 45
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 36
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 229910006587 β-Al2O3 Inorganic materials 0.000 claims description 13
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 11
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 35
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- 230000005611 electricity Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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
- C25C3/18—Electrolytes
Abstract
The present invention discloses alumina dissolution speed method in a kind of quickening aluminium cell, belongs to the field of aluminum electrolysis of nonferrous metallurgy.The method of the invention, which uses, contains β Al2O3Na2O·xAl2O3（X values are 6 ~ 50）For aluminium electroloysis raw material, the electrolyte principal component used is NaF AlF3；AlF is added in into electrolyte in electrolytic process3Neutralize the Na generated after alumina dissolution2O, to maintain the stable components of electrolyte, electrolysis temperature is 680 900 DEG C.Solution rate is slow in the electrolyte for aluminium oxide during the present invention solves the problems, such as low-temperature aluminum electrolysis, can be used on aluminium cell of traditional aluminium cell either using inert anode, realize low temperature（680‑900℃）Aluminium electroloysis reaches the target of energy-saving and emission-reduction.
Description
Technical field
The present invention relates to alumina dissolution speed method in a kind of quickening aluminium cell, the aluminium electroloysis for belonging to nonferrous metallurgy is led
Domain.
Background technology
Traditional aluminium cell running temperature is higher, is 910 ~ 970 DEG C, electrolytic cell distributes substantial amounts of heat in electrolytic process
Amount, makes the utilization rate of electrical of electrolytic cell be less than 50%, the energy consumption for causing aluminium electroloysis is higher.100 for many years, Aluminium Industry
It constantly explores and saves power consumption, improve working conditions, reduce ton aluminium production cost, increase the various ways of single slot aluminium yield
Footpath.It is one of optimal path wherein to reduce electrolysis temperature.Low-temperature aluminum electrolysis（Electrolysis temperature is 680-850 DEG C）Be conducive to improve electricity
Efficiency is flowed, extends bath life, it is often more important that low-temperature aluminum electrolysis is conducive to insulation sides lining material and inertia non-carbon anode and cathode
Material is applied on the thermal-insulating type electrolytic cell of new structure, so as to fulfill the energy-saving and emission-reduction and sustainable development of aluminum i ndustry,
It is final to realize green aluminium electroloysis.Low-temperature aluminum electrolysis is since electrolysis temperature is relatively low, and the molecular proportion of electrolyte is relatively low, causes oxygen
Changing the solubility of aluminium reduces, and solution rate is very slow.The concentration general control of aluminium oxide in a cell is in 2-3%, low-temperature electrolytes
The solubility of middle aluminium oxide generally above 2% can reach the concentration requirement of aluminium oxide in electrolytic cell.Therefore low-temperature aluminum electrolysis
The problem of maximum faced is that alumina dissolution speed is slow, this can aggravate anode for the electrolytic cell using inert anode
Corrosion, shortens anode life, and makes primary aluminum deterioration, and then can be frequent for the electrolytic cell using carbon annode
Appearance anode effect, and there is many slot bottoms precipitation, prevent electrolysis from being smoothed out.Therefore low-temperature aluminum electrolysis needs solve
Greatest problem is exactly the slow-footed problem of alumina dissolution.
In order to solve the problems, such as that alumina dissolution is slow-footed, the Aluminum Manufacturers technology company in the U.S. adds in quality into electrolyte
Than being electrolysed for the suspension alumina powder that 10% average grain diameter is 1 μm, in the alumina powder containing a large amount of γ-
Al2O3, in addition granularity is smaller, specific surface area is larger, accelerates the solution rate of aluminium oxide in the electrolyte, while avoids aoxidizing
Aluminium forms a large amount of precipitations in bottom of electrolytic tank, but this method undoubtedly can decline the electrical conductivity of electrolyte, tank voltage rise, most
Disadvantageously the levigate process of increase aluminium oxide is needed, greatly increases cost, commercial Application is affected.
The content of the invention
The technical problem to be solved by the present invention is to：Solution rate is slow in the electrolyte for aluminium oxide during low-temperature aluminum electrolysis
Problem.
It is an object of the invention to provide a kind of methods for accelerating alumina dissolution speed in aluminium cell, can be used for passing
The aluminium cell of system either using in the aluminium cell of inert anode, realizes low temperature（680-900℃）Aluminium electroloysis reaches energy saving
The target of emission reduction, specifically includes：With Na2O·xAl2O3For raw material, the main component of electrolyte is NaF-AlF3, in electrolytic process
Middle addition AlF3Adjust the stable components of electrolyte, the AlF of addition3With Na2O·xAl2O3Mass ratio be 56/（62+102x）.
Na of the present invention2O·xAl2O3In x values for 6 ~ 50, i.e. Al2O3With Na2The molal quantity ratio of O is 1:6~1:
50, Na2O·xAl2O3In contain β-Al2O3, β-Al2O3In Na2O·xAl2O3In mass percent be 10-90wt%.
NaF mass percents are 34-48wt%, Al in electrolyte of the present invention2O3Mass percent is 1.5-4wt%, electricity
It solves content of impurities in matter and is no more than 16wt%, surplus AlF3。
Impurity of the present invention is CaF2、LiF、KF、MgF2In one or several kinds, CaF2Mass percent is 0-
5wt%, LiF mass percent are 0-5wt%, and KF mass percents are 0-5wt%, MgF2Mass percent is 0-2wt%.
Electrolysis temperature of the present invention is 680-900 DEG C.
Beneficial effects of the present invention：
（1）Present invention reduces aluminium electrolytic temperatures, it is possible to reduce the radiation loss of electrolytic cell increases substantially the electric energy of aluminium electroloysis
Efficiency.
（2）Due to accelerating the solution rate of aluminium oxide, no dissolving during low-temperature aluminum electrolysis can be effectively reduced
Aluminium oxide forms the phenomenon that slot bottom precipitation.
（3）Present invention reduces electrolysis temperatures, using the lower electrolyte of molecular proportion, can obtain higher electric current effect
Rate.
（4）Due to reducing aluminium electrolytic temperature, the use that the present invention is inert anode in aluminium cell provides possibility,
And the zero-emission of aluminium electrolysis process greenhouse gases can be realized by substituting existing consumptive carbon anode using inert anode.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment, but protection scope of the present invention is not limited to
The content.
It is tested in all embodiments of the invention using carbon anode.
Embodiment 1
Use Na2O·40Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt15%；Electrolyte it is main into
It is divided into NaF-AlF3, wherein, the mass percent of aluminium oxide is 4wt%, CaF2Mass percent is 5wt%, LiF mass percents
For 5wt%, KF mass percents are 5wt%, MgF2Mass percent is 1wt%, and NaF mass percents are 40wt%, and surplus is
AlF3；AlF is added in electrolytic process3Neutralize the Na generated2O, AlF3With Na2O·30Al2O3The mass ratio of raw material is
0.0135, electrolysis temperature is 880-900 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, is precipitated without slot bottom, anode effect does not occur；And make
With industrial Al2O3Carry out phenomena such as electrolysis is present with voltage fluctuation, slot bottom precipitation is more.
Embodiment 2
Use Na2O·6Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt90%；The main component of electrolyte
For NaF-AlF3, wherein, the mass percent of aluminium oxide is 1.5wt%, and NaF mass percents are 35wt%, surplus AlF3；
AlF is added in electrolytic process3Neutralize the Na generated2O, AlF3With Na2O·6Al2O3The mass ratio of raw material is 0.084, electrolysis temperature
For 690-710 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is seldom, and anode effect is less prone to；And make
With industrial Al2O3Carry out electrolysis be present with voltage fluctuation, slot bottom precipitation it is more, frequently occur phenomena such as anode effect, can not be normal
Electrolysis.
Embodiment 3
Use Na2O·11Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt70%；Electrolyte it is main into
It is divided into NaF-AlF3, wherein, the mass percent of aluminium oxide is 2wt%, CaF2Mass percent is 5wt%, LiF mass percents
For 1wt%, NaF mass percents are 32.5wt%, surplus AlF3；AlF is added in electrolytic process3Neutralize the Na generated2O,
AlF3With Na2O·11Al2O3The mass ratio of raw material is 0.047, and electrolysis temperature is 680-700 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is few, the less generation of anode effect；And it uses
Industrial Al2O3Carry out electrolysis be present with voltage fluctuation, slot bottom precipitation it is more, frequently occur phenomena such as anode effect, can not normally electricity
Solution.
Embodiment 4
Use Na2O·20Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt40%；Electrolyte it is main into
It is divided into NaF-AlF3, wherein, the mass percent of aluminium oxide is 2wt%, CaF2Mass percent is 5wt%, LiF mass percents
For 1wt%, NaF mass percents are 39.4wt%, surplus AlF3；AlF is added in electrolytic process3Neutralize the Na generated2O,
AlF3With Na2O·11Al2O3The mass ratio of raw material is 0.027, and electrolysis temperature is 790-810 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is few, and anode effect does not occur；And it uses
Industrial Al2O3Carry out electrolysis be present with voltage fluctuation, slot bottom precipitation it is more, frequently occur phenomena such as anode effect, can not normally electricity
Solution.
Embodiment 5
Use Na2O·25Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt20%；Electrolyte it is main into
It is divided into NaF-AlF3, wherein, the mass percent of aluminium oxide is 2wt%, CaF2Mass percent is 5wt%, LiF mass percents
For 5wt%, KF mass percents are 5wt%, and NaF mass percents are 39.3wt%, surplus AlF3.It is added in electrolytic process
AlF3Neutralize the Na generated2O, AlF3With Na2O·11Al2O3The mass ratio of raw material is 0.021, and electrolysis temperature is 850-870 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is few, and anode effect does not occur；And it uses
Industrial Al2O3Carry out phenomena such as electrolysis is present with voltage fluctuation, slot bottom precipitation is more, anode effect is more.
Embodiment 6
Use Na2O·15Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt50%.Electrolyte it is main into
It is divided into NaF-AlF3, wherein, the mass percent of aluminium oxide is 3wt%, CaF2Mass percent is 4wt%, LiF mass percents
For 4wt%, KF mass percents are 4wt%, and NaF mass percents are 31.9wt%, surplus AlF3；It is added in electrolytic process
AlF3Neutralize the Na generated2O, AlF3With Na2O·11Al2O3The mass ratio of raw material is 0.035, and electrolysis temperature is 680-700 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is few, and anode effect does not occur；And it uses
Industrial Al2O3Carry out electrolysis be present with voltage fluctuation, slot bottom precipitation it is more, frequently occur phenomena such as anode effect, can not normally electricity
Solution.
Embodiment 7
Use Na2O·20Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt40%；Electrolyte it is main into
It is divided into NaF-AlF3, wherein, the mass percent of aluminium oxide is 2wt%, CaF2Mass percent is 4wt%, LiF mass percents
For 1wt%, NaF mass percents are 36.6wt%, surplus AlF3；AlF is added in electrolytic process3Neutralize the Na generated2O,
AlF3With Na2O·11Al2O3The mass ratio of raw material is 0.027, and electrolysis temperature is 710-730 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is few, the less generation of anode effect；And it uses
Industrial Al2O3Carry out electrolysis be present with voltage fluctuation, slot bottom precipitation it is more, frequently occur phenomena such as anode effect, can not normally electricity
Solution.
Embodiment 8
Use Na2O·50Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt10%；The master of the electrolyte
It is NaF-AlF to want ingredient3, wherein, the mass percent of aluminium oxide is 3wt%, CaF2Mass percent is 5wt%, LiF mass hundred
Divide than being 1wt%, KF mass percents are 5wt%, MgF2Mass percent is 1wt%, and NaF mass percents are 43.3wt%, remaining
It measures as AlF3；AlF is added in electrolytic process3Neutralize the Na generated2O, AlF3With Na2O·30Al2O3The mass ratio of raw material is
0.011, electrolysis temperature is 880-900 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is seldom, the less generation of anode effect；And make
With industrial Al2O3Carry out phenomena such as electrolysis is present with voltage fluctuation, slot bottom precipitation is more, anode effect easily triggers.
Embodiment 9
Use Na2O·50Al2O3For aluminium electroloysis raw material, wherein β-Al2O3Mass percent is wt10%；The master of the electrolyte
It is NaF-AlF to want ingredient3, wherein, the mass percent of aluminium oxide is 2wt%, and NaF mass percents are 49wt%, and surplus is
AlF3；AlF is added in electrolytic process3Neutralize the Na generated2O, AlF3With Na2O·30Al2O3The mass ratio of raw material is 0.011,
Electrolysis temperature is 880-900 DEG C.
Electrolytic cell normal operation in the present embodiment, voltage is steady, and slot bottom precipitation is seldom.And use industry Al2O3It is electrolysed
It is present with voltage fluctuation, slot bottom precipitates phenomena such as more, anode effect easily triggers.
Claims (5)
- A kind of 1. method for accelerating alumina dissolution speed in aluminium cell, it is characterised in that：With Na2O·xAl2O3For raw material, The main component of electrolyte is NaF-AlF3, AlF is added in electrolytic process3Adjust the stable components of electrolyte, the AlF of addition3 With Na2O·xAl2O3The mass ratio of raw material is 56/（62+102x）.
- 2. accelerate the method for alumina dissolution speed in aluminium cell according to claim 1, it is characterised in that：Na2O· xAl2O3In x values be 6 ~ 50, Na2O·xAl2O3In contain β-Al2O3, β-Al2O3In Na2O·xAl2O3In mass percent For 10-90wt%.
- 3. accelerate the method for alumina dissolution speed in aluminium cell according to claim 1, it is characterised in that：In electrolyte NaF mass percents are 31.9-49wt%, Al2O3Mass percent is 1.5-4wt%, and the total content of impurity is remaining not higher than 16wt% It measures as AlF3。
- 4. accelerate the method for alumina dissolution speed in aluminium cell according to claim 4, it is characterised in that：Impurity is CaF2、LiF、KF、MgF2In one or several kinds, CaF2Mass percent is 0-5wt%, and LiF mass percents are 0-5wt%, KF mass percents are 0-5wt%, MgF2Mass percent is 0-2wt%.
- 5. accelerate the method for alumina dissolution speed in aluminium cell according to claim 1, it is characterised in that：Electrolysis temperature For 680-900 DEG C.
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| CN108950603A (en) * | 2018-08-31 | 2018-12-07 | 营口忠旺铝业有限公司 | A kind of method for electrolyzing aluminum improving electrolyte dissolution degree |
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