The field of application.
[0001] The invention pertains to the technique of producing metals by electrolysis. More
specifically, it relates to the methods of producing metals by electrolysis while
using the liquid-metallic cathode.
[0002] In molten electrolytes, such a technique is used for producing aluminium, alloys
of alcali and alcaline-earth metals with lead and copper. The amalgam of sodium is
obtained on the mercury cathode in the water solutions of sodium chloride.
The current state of the technique.
[0003] The use of the liquid-metallic cathode in electrolytic cells is combined with the
use of the anodes, the working surface of which is horizontal and faces downwards.
Under such a surface there forms a powerful gas-liquid flow and the efficiency of
modern electrolytic cells with the liquid-metallic cathode depends on the solution
of the problem of controlling the gas fluid dynamics of the electrolysis.
[0004] One of the known suggestions to solve this problem is the removal of anodic gases.
This can be realised by providing tubes in the anodes ( DE-Patent No 817529, US-Patent
No 2917441) or by perforating the anodes (US Patent No 3714002).
[0005] Another known suggestion to control the gas fluid dynamics of the electrolysis is
the reduction of the anodic effect occurence by applying oscillations or small amplitudes
to the anode (France Patent No 2083362). The reduction of the gas content in an electrolytic
cell can be achieved, for exemple, by applying pendulum-like oscillations to the anode
(US Patent No 3501386).
[0006] However, the solutions cited above as well as a number of other solutions have not
come into use mainly because of problems in designing due to aggressive media and
high temperatures. Those suggestions, which were employed on an industrial scale,
proved to be little efficient in controlling the gas fluid dynamics of electrolysis.
[0007] Another important shortcoming inherent in an electrolytic cell with the liquid-metallic
cathode and the horizontal anode is feed problems in the electrolysis of aluminium,
where the cryolite-alumina melt is used as an electrolyte. Thus, in the known technique
(J.Thonstad, Aluminium electrolysis, electrolyte electrochemistry Advances in molten
salt chemistry. Amsterdam-Oxford-New-York-Tokio, 1987, p.73-126) the electrolyte crust
with alumina deposited on it has to be broken by special devices 10 and more times
a day. This causes pieces of the crust and alumina to get into the liquid electrolyte.
Some other solutions envisage different kinds of devices for the continuous feed of
alumina to electrolytic cells without the breakage of the electrolyte crust or only
with the partial one. The technique comprising the frequent breakage of the electrolyte
crust is accompanied by a periodic loss of the tightness of a cell and an additional
escape of fluoric hydrogen, aluminium and sodium fluorides.
[0008] The continuous feed to electrolytic cells by means of mounting special feeding devices
on the bath envolves great capital and maintenance costs and reduces the total economic
efficiency of the electrolysis.
The description of the invention.
[0009] The aim of this invention is to raise the efficiency of the electrolysis.
[0010] The authors came upon the fact that, if the level of the electrolyte is kept possibly
minimal and equal to one or two-fold value of the interpolar distance (IPD), the metal
loss decreases and the cathode current efficiency increases while the unit escape
of toxic substances, including cancer-causing polyaromatic hydrocarbons, per a ton
of produced metal goes down. Thus, both the efficiency of electrolytic cells and the
ecological acceptability of the process are improved.
[0011] The investigations on the gas fluid dynamics of the electrolysis, carried out by
the authors, showed that the metal loss occur mainly through the dispersion in the
electrolyte from the crest of the standing wave which is situated at the anode and
the side carbon near the anodic edge. The lowering of the electrolyte level to one
or two-fold value of the IPD reduces the velocities of electrolyte flows that cause
the metal dispersion.
[0012] Another problem being solved by this invention is the simplification of the feeding
process and feeding devices. It is suggested to feed a cell by means of periodic vertical
movements of the anode. The alumina is poured down into the electrolyte through the
slot along the perimeter of the anode.
[0013] When the alumina stays on the unbroken crust for a long time, it may loose some of
its absorptivity. To avoid this, the whole crust may by periodically, say once every
5-10 days, broken by the conventional method and large quantities of fresh alumina
may by fed to a cell.
[0014] The examples of the realisation of the invention.
Example 1.
[0015] The fields of the electrolyte velocities were studied on the physical model of a
vertical cross-cut of a H.Z. aluminium electrolytic cell when the anode width is 2m,
the anodic current density is 6920 A/m², the levels of the electrolyte are 20 and
8cm for the IPD of 6cm.
[0016] The data obtained is shown in Table 1.
Table 1
Solutions compared |
Electrolyte level |
Maximum averaged velocity mm/sec |
Horizontal dimension on the vortex mm |
|
cm |
fractions of the IPD |
|
|
Conventional |
20 |
3.33 |
200 |
350-400 |
Suggested |
8 |
1.33 |
100 |
100-150 |
[0017] Thus, the characteristics of the vortex that determines the gas fluid dynamic share
of the metal loss become more favourable.
Example 2.
[0018] The data given in Table 2 was obtained in the electrolysis of the system, comprising
lead and potassium chlorides, with the lead cathode and the graphite anode at a temperature
of 700°C, a cathode current density of 0.5A/cm², the IPD of 2cm and the anode width
of 160mm.
Table 2
Solutions compared |
Electrolyte level |
Lead output current efficiency % |
|
Cm |
fractions of the IPD |
|
Conventional |
12 |
6.0 |
68 ± 3 |
Suggested |
3 |
1.5 |
97 ± 3 |
[0019] As can be seen, the use of the minimum levels of the electrolyte allows to minimize
the metal loss and raise the current efficiency to the maximum values. The data quite
agrees with the correlation, well known in the aluminium industry, between the current
efficiency and the quantity of metal in a cell. With a given depth of the bath, the
increase in the level of metal leads to the decrease of the level of electrolyte.
It is due to the latter factor that the metal loss is reduced. The greatest effect
can be achieved by employing the suggested solution.
Example 3.
[0020] On the group of 5 industrial aluminium V.Z. cells at a current of 155kA the feed
of raw materials was performed via the vertical oscillations of the anode under the
following conditions:
1. The lift of the anode was effected to 450mv of the ohmic resistance of the interpolar
gap.
2. The anode was lowered to the initial position.
3. The lift was repeated.
4. The lowering was repeated.
[0021] Such a vertical displacement of the anode was performed twice a shift, i.e.,once
every 3 hours. The alumina was, thus, fed into a cell through the slot being formed
between the bell-shaped gas collector and the crust and through a few number of local
cavings of the electrolyte crust. The slot and cavings were made tight by pouring
the alumina over them. The frequency of anodic effects on the tested baths during
a week was 0.25 per day while on the control ones it was 1.7, which proves a high
efficiency of the suggested solution. There were no cases of accumulation and formation
of the sediments on the cell bottom. The redistribution of the alumina feeding over
the whole perimeter of the anode allows to maintain the minimum levels of the electrolyte.
The industrial applicability.
[0022] The industrial applicability of the invention to be patented is determined by the
fact that its introduction does not require any essential design changes in the cells
being used now. No additional devices are needed either to maintain the electrolyte
level or to feed cells. The vertical movements of the anode for feeding raw materials
into a cell can be realised through the conventional devices for regulating the anode
position.
[0023] The employment of the invention to be patented possesses the following advantages
as compared to the conventional methods:
1. The cathode current efficiency rises to 96-97 per cent and more.
2. The consumption of materials and power is reduced.
3. The full automatization of the procces becomes a possibility.
4. The escape of toxic substances into the atmosphere from the anodes of H.Z. and
V.Z. aluminium cells is reduced.
5. It becomes possible to modernize the outdated aluminium plants equipped with Soderberg
cells.
[0024] The H.Z. and V.Z. baths can reach a 92-95 per cent current efficiency, i.e., the
values obtained on the most recent P.A. cells. If the invention is introduced in the
latter type of cells, the current efficiency can be raised to 96-98 per cent.