U.S. patent number 3,625,842 [Application Number 04/731,901] was granted by the patent office on 1971-12-07 for alumina feed control.
This patent grant is currently assigned to Kaiser Aluminum and Chemical Corporation. Invention is credited to Donald R. Bristol, Joseph G. C. Simard, also known as J. G. Clement Simard.
United States Patent |
3,625,842 |
Bristol , et al. |
December 7, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
ALUMINA FEED CONTROL
Abstract
A method of controlling the feeding of alumina to a reduction
cell for the production of aluminum. The method comprises obtaining
several measurements of the voltage across the cell and current to
the cell and deriving from the measurements an average resistance
level for the cell which will be referred to as a base level. A
smoothed resistance is derived from several sequential measurements
of the voltage and current. When the smoothed resistance exceeds
the base resistance level by more than an assigned limit, a
controlled amount of alumina is added to the cell.
Inventors: |
Bristol; Donald R. (Orinda,
CA), Joseph G. C. Simard, also known as J. G. Clement Simard
(Ravenswood, WV) |
Assignee: |
Kaiser Aluminum and Chemical
Corporation (Oakland, CA)
|
Family
ID: |
24941386 |
Appl.
No.: |
04/731,901 |
Filed: |
May 24, 1968 |
Current U.S.
Class: |
205/336; 204/245;
204/225; 205/392 |
Current CPC
Class: |
C25C
3/20 (20130101) |
Current International
Class: |
C25C
3/20 (20060101); C25C 3/00 (20060101); C22d
003/12 () |
Field of
Search: |
;204/67,245,225 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Valentine; D. R.
Claims
What is claimed is:
1. A method of controlling the feeding alumina to a reduction cell
having an anode adjustably movable toward and away from the cathode
comprising the following steps which are carried out over a
predetermined cycle for the cell:
a. periodically measuring the voltage and current of the cell
throughout the cycle,
b. determining the cell resistance R.sub.M from the equation
R.sub.M =V-- A/I where
V is the measured cell voltage
I is the measured cell current, and
A is a predetermined back electromotive force
c. determining a lowest resistance level R.sub.B by periodically
determining a base level resistance R.sub.B by a smoothing
technique from a series of R.sub.M values determined over a first
interval of time,
d. periodically determining a resistance R.sub.S by a smoothing
technique from a series of R.sub.M values over a second interval of
time,
e. providing comparator means for automatically comparing the
R.sub.S value with the lowest preceding R.sub.B value during said
cycle, and
f. feeding alumina to said cell in response to said comparator
means when the difference between the R.sub.S value and the lowest
R.sub.B value exceeds a predetermined limit.
2. The method of claim 1 wherein said first interval of time is
greater than said second interval of time.
3. The method of claim 1 including the step of adjusting the
distance between the anode and cathode following the addition of
alumina to the cell.
Description
BACKGROUND OF THE INVENTION
The metal aluminum is extracted from aluminum bearing compounds
such as alumina (Al.sub.2 O.sub.3) by electrolysis from a molten
cell bath or electrolyte. In the production of aluminum by the
conventional electrolytic process, commonly referred to as the
Hall-Heroult Process, the electrolytic cell comprises in general a
steel shell having disposed therein a carbon lining. The bottom of
the carbon lining, together with a layer of electrolytically
produced molten aluminum which collects thereon during operation,
serves as the cathode. One or more consumable carbon electrodes is
disposed from the top of the cell and is immersed at its lower
extremity into a layer of molten electrolyte which is disposed in
the cell and above the molten alumina layer. In operation, the
electrolyte or bath which is basically a mixture of alumina and
cryolite is charged to the cell and an electric current is passed
through the cell from the anode to the cathode via the layer of
molten electrolyte. The alumina is dissociated by the current so
that aluminum is deposited on the liquid aluminum cathode and
oxygen is liberated at the carbon anode, forming carbon monoxide
and carbon dioxide gas. A crust of solidified electrolyte and
alumina forms on the surface of the bath, and this is usually
covered over with additional alumina.
In the conventional electrolytic process, use has been made of two
types of electrolytic cells, namely that commonly referred to as a
"prebake" cell and that commonly referred to as a "Soderberg" cell.
With either cell, the reduction process involves precisely the same
chemical reactions. The principal difference is one of structure.
In the prebake cell, the carbon anodes are prebaked before being
installed in the cell, while in the Soderberg, or self-baking anode
cell, the anode is baked in situ, i.e., it is baked during
operation of the electrolytic cell, thereby utilizing part of the
heat generated by the reduction process. The instant invention is
applicable to either cell.
A typical aluminum electrolytic bath used in commercial
installations might have the following composition:
1- 10 percent alumina, usually about 6 percent in conventional
American practice,
0- 10 percent aluminum trifluoride,
5-12 percent calcium fluoride, and
80-90 percent cryolite.
As the electrolysis continues, alumina is consumed in direct
proportion to the metal production. As the alumina concentration in
the electrolyte is reduced, a point is reached where a troublesome
phenomenon known as "anode effect" occurs. The voltage drop across
the cell can increase, for example, from around 4 volts to as much
as 40 volts and even higher. This effect is generally attributed to
too low a concentration of alumina in the reduction cell bath or
electrolyte. The actual concentration of alumina in the electrolyte
at which this effect occurs seems to depend upon the temperature,
the composition of the electrolyte and the anode current density,
but usually is somewhat below about 2 percent by weight. The
occurrence of an anode effect is the signal for the addition of
more alumina. The attendant does this by breaking the frozen crust
on top of which he has previously distributed a layer of alumina.
The addition of the alumina, accompanied by a vigorous stirring of
the electrolyte, causes the anode effect to disappear, after which
the electrolysis continues its normal course until the next anode
effect occurs.
There are several disadvantageous results of an anode effect such
that minimizing or substantially eliminating or controlling the
duration of their occurrence is desirable. According to one theory,
during the normal course of electrolysis, the effective surface of
the anode is believed to be surrounded by gas bubbles which are
constantly escaping from it. They are believed to form on the
anode, break away easily, and escape from the electrolyte. Smooth
evolution of gas around the anode is believed to be a sign of
normal operation. The moment the anode effect occurs, according to
this theory, the effective surface of the electrode is believed to
be entirely surrounded by a film of gas. This is believed to cover
the surface of the anode and push the fused electrolyte away,
producing the so-called "nonwetting" of the anode. Small arcs are
thought to form between the electrolyte and the anode. Complete
interruption of the current is not believed to occur, as some
current is thought to be carried by these continually shifting
arcs. The arcs are believed to cause local heating, volatilizing
some bath material and producing sufficient gas so that the
individual arcs are almost immediately broken.
New arcs are believed to form, as the bath film near the anode must
necessarily be uneven in character, and momentary contacts are
thought to take place between the anode and the bath. The
overheating that occurs during anode effect causes excessive
consumption of the anode, excessive consumption of electrolyte by
volatilization, and results in a lowered yield of product. A very
important result of the anode effect is a large, unproductive power
consumption.
With the developing trend toward more automated cell operation, the
control of alumina concentration in the bath or electrolyte through
cell feeding has become quite important. In most cell control
schemes, it is desired that the number and severity of anode
effects be minimized without overfeeding the cell. This involves
either controlling the feed rate or measuring the concentration of
the alumina in the bath or electrolyte or in some way receiving an
indication of incipient anode effects so that a substantially
constant alumina concentration can be maintained. The prior art
describes many methods which have been utilized in the past to
determine the alumina concentration in the electrolyte or bath or
to obtain some sort of prewarning of an oncoming anode effect.
These methods include chemical analysis for the alumina
concentration, either by pyrotitration techniques, caustic leach
methods, gravimetric methods of analysis, volumetric methods of
analysis, or by means of electrical conductivity measurements.
Examination of physical properties of the electrolyte has also been
utilized to some extent. The appearance of the electrolyte, both
molten and solidified, has been compared with known samples;
crystalline phases have been examined by microscope and X-ray
diffraction, as well as in other ways. None of these prior art
methods have been truly satisfactory. Those methods with high
accuracy and reliability take too long to yield the desired
information. Techniques which produce an answer more rapidly, tend
to be rather inaccurate.
One important approach to the problem of detecting the oncoming of
an anode effect is outlined in an article by McMahon, T. K., and
Dirth, G. P., "Computer Control of Aluminum Reduction Cells,"
Journal of Metals, Vol. 18, No. 3, pp. 317-319, March 1966. The
approach outlined therein involves measuring the total voltage drop
across the cell, from collector bar of one cell to collector bar of
the next, computing the total cell resistance from this and noting
when the resistance starts to rise rapidly. This signifies the
oncoming of an anode effect and the anode effect termination
procedure is then initiated and hopefully the occurrence of an
anode effect is avoided.
This procedure, theoretically, is useful in avoiding anode effects
and in controlling the alumina concentration, but the resistance
curve produced by the measurements suggested by McMahon et al. is
quite sensitive to noise or electrical interference in the
circuitry and in the cell itself. This noise or interference can
sometimes result in a short, sharp temporary rise in the resistance
curve which is a false indication of the oncoming of an anode
effect.
The instant invention was developed against this background in the
art.
SUMMARY OF THE INVENTION
It is an advantage of the instant invention that it will minimize
the effect of electrical and process noise and interference on the
cell resistance curve. By smoothing the curve and screening out
interference the possibility of a false signal of an incipient
anode effect is minimized. Accordingly, the system will be more
accurate.
It is a further advantage of the instant invention that the alumina
concentration can be maintained in a range known as "lean feed,"
hereinafter defined.
The feed is controlled for two purposes. One is to avoid anode
effects and the other, desirably, is to maintain a substantially
constant alumina concentration in the cell which results in
improved efficiency of the reduction process. Several measurements
of the voltage drop across the cell and the current to the cell are
obtained. This is normally done by connecting a suitable voltage
indicating instrument between the collector bars of one cell and
the collector bars of the next or between the anode and the cathode
bus bars of a cell and a suitable amperage indicating instrument in
series with the power supply. A resistance for the cell is derived
from these measurements according to the relationship:
R.sub.M =V-A/I (i)
where R.sub.M is the resistance in ohms,
V is the normal voltage drop across the cell in volts,
I is the current to the cell in amperes, and
A is the back electromotive force in volts.
The resistance level R.sub.B for the cell will be referred to as a
base level. The resistance level for the cell desirably is
periodically redetermined from fresh voltage measurements and the
new resistance level is used as a base level if lower in value than
the previous base level. A smoothed resistance R.sub.S is derived
from several sequential measurements of the voltage and current.
Smoothing techniques are well known to those skilled in the art.
This may be done mathematically by determining the trend in the
voltage drop and hence the resistance from these measurements and
projecting what the next measurement of the voltage and hence the
next value of the resistance should be, or other appropriate
smoothing techniques to reduce the effect of electrical noise and
static may be employed. Hence, by "smoothed" is meant any such
technique, mathematical, electrical, mechanical or any combination
thereof. In practice a predictor form of smoothing technique has
been found to be more desirable than simple averaging. A suitable
smoothing technique which can be used as a prediction has been
described by Box, G. E. P., and Jenkins G. N., "Some Statistical
Aspects of Adaptive Optimization and Control," The Journal of The
Royal Statistical Society, Series B (Methodological), pp. 297-343,
Vol. 24, No. 2, 1962. When the smoothed resistance R.sub.S exceeds
the base resistance level by more than an assigned limit, a
controlled amount of alumina is added to the cell. This normally
lowers the resistance level R.sub.B of the cell and the cycle of
operations restarts.
The procedure of always using the lowest value of the resistance as
a base level makes it possible to keep the control of the alumina
concentration in the lean feed range. It has been found that the
alumina concentration wherein the optimum efficiency of operation
of the reduction cells, as measured by the current efficiency of
the cells, occurs seems to be quite close to the level at which an
anode effect occurs. When an anode effect occurs, the cell reaction
is believed according to one theory to change from a decomposition
of alumina to a decomposition of the aluminum fluoride in the bath.
Thus, the alumina concentration should be maintained by this
process above the value at which the decomposition voltage for
aluminum fluoride seems to be attained, the aluminum fluoride
reacting to form carbon tetrafluoride with the anode, but at the
same time close to it. The precise alumina concentration at which
the decomposition voltage for aluminum fluoride seems to be
obtained will vary somewhat from cell to cell but should always be
below about 4 percent by weight. Desirably, the alumina
concentration should be maintained below about 3 percent by weight.
More specifically, in the normal American reduction cell, the
alumina concentration should be maintained from about 2 percent to
about 3 percent by weight.
Should an adjustment in the anode-cathode distance to the desired
operating level be necessary, this should be done before obtaining
the voltage and current measurements so that the cell resistance
curve can stabilize after the anode-cathode distance adjustment
before the voltage and current measurements and the resistance
level determination. From this it also follows that the
anode-cathode distance should desirably be maintained constant
while obtaining the voltage and current measurements.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic showing of a computer controlled potline.
FIG. 2 is a typical graph of predicted resistance in micro ohms
versus time illustrating the principles of the instant
invention.
DETAILED DESCRIPTION
The article by McMahon and Dirth mentioned above discusses the
control scheme for reduction cells which is based on measuring the
total resistance across the cell. The basic relationships between
resistance and feed concentration discussed therein are applicable
in the following discussion.
The authors thought that there were three short term variables in
the total resistance; the anode-cathode distance, specific bath
resistivity, and resistance of the gas film surrounding the anode.
The authors felt that both the bath resistance and the film
resistance were affected by the alumina concentration. However, in
reality, assuming constant anode-cathode distance, the cell
resistance is then determined by what may properly be described as
two factors. One of these is the bath or electrolyte resistance and
the other is best characterized as the back electromotive force
(EMF).
The back electromotive force is not properly a pure resistance in
that it involves the decomposition potential for the reaction of
the alumina and the cathode gas film polarization and the anode gas
film polarization as well as some other small variables. The
McMahon article assumed that the decomposition potential was a
constant. In reality it is not. It has been discovered that the
back electromotive force builds up constantly as the alumina
concentration in the electrolyte decreases. Although the factors
influencing it are not precisely known, the optimum value of back
EMF, that is the value that optimizes cell productivity, seems to
vary from cell to cell. One can determine the optimum value of back
EMF for a cell by evaluating its efficiency at various back EMF
levels.
One determines an average resistance level for the cell from
several measurements of the voltage drop across the cell and the
current to the cell as has been discussed previously. This average
resistance for the cell is referred to as a base level. This
operation and the other determinations and derivations involved in
the instant process may be done manually, but the process is
particularly adaptable to computerization. There are many process
control computers available which can be used for this. One such
computer is that known in the trade as a GE/PAC 40501. This
computer is specifically designed for process control and real time
operation. A typical computer of this type has a core size of
12,000 24-binary bit words. It has a memory cycle speed of 5
microseconds with no bulk memory. The inputs to the computer
comprise three groups of 20 digital inputs, ten groups of 16 analog
inputs, one paper tape reader with the capability of 100 characters
per second, and one operator console. The outputs from the computer
comprise eight groups of 16 digital outputs, one paper tape punch
with a capacity of 120 characters per second, and two remote
console output typewriters. Using the computer the entire operation
can be done much more rapidly and values can be determined and used
while still representative of the cell conditions.
The average resistance level for the cell is periodically
redetermined from fresh voltage and current measurements, and the
new average resistance level is used as a base level if lower in
value than the previous base level. It has also been mentioned
previously that a smoothed resistance is derived from several
sequential measurements of the voltage and current and when the
smoothed resistance exceeds the base level resistance by more than
an assigned limit a controlled amount of alumina is added to the
cell to bring the concentration and resistance value back into the
desired range.
It has recently been found the greatest current efficiency in a
reduction cell seems to occur when the cell is operating on what
may be called a "lean feed." A lean feed may be defined as a
quantity of alumina in the bath just sufficient to prevent the cell
from going on anode effect. While the operating characteristics of
the cell, such as temperature, depth of electrolyte, anode-cathode
spacing, etc., may affect this value, it can be expressed in terms
of decomposition (polarization) potentials. Sufficient alumina is
maintained in the cell to prevent the resistance in the cell from
building up until the voltage reaches the value for the
decomposition of the aluminum fluoride to form carbon tetrafluoride
in a reaction with the carbonaceous anode. Thus the alumina
concentration must be maintained above the value at which the
decomposition voltage for aluminum fluoride is attained but close
to it. The allowable differential for the smoothed resistance from
the base resistance level can be used to do this. A useful upper
limit on concentration would seem to be about 4 percent by weight.
The utilization of the lowest value of the average resistance as a
base level at all times will assure that the control is on the lean
side of 4 percent alumina concentration in the bath by weight. A
preferred upper limit would be about 3 percent by weight, and
perhaps the optimum concentration would be from 2 percent to about
3 percent by weight. Since the smoothed resistance curve is
sensitive to changes in alumina concentration quite close to the
anode effect concentrations, it can be used to maintain the alumina
concentration in these ranges.
With reference now to FIG. 1 which shows a computer controlled
potline in schematic form, it may be seen that the cell comprises
first a metal shell 10, generally steel, within which is disposed
in the usual manner an insulating layer 12 which can be any desired
material, e.g., alumina, bauxite, clay, aluminum silicate brick,
etc. Within the insulating layer 12 is disposed cell lining 14
which can be of any desired material, e.g., carbon, alumina, fused
alumina, silicon carbide, silicon nitrate bonded silicon carbide,
or other desired materials. Most commonly, the lining is made up of
a plurality of carbon blocks or is a rammed carbon mixture or a
combination of a rammed carbon mixture for the bottom of the lining
with side and end walls constructed of carbon. Alternatively, the
side and end walls can be constructed of blocks of silicon carbide
or other suitable refractory. The lining 14 defines a chamber which
contains a pool of molten aluminum 16 and a body of molten
electrolyte or bath 18 as described.
Suspended from above the electrolyte and partially immersed therein
are anodes 20 of the conventional carbon type and shown here as a
prebaked anode. The molten electrolyte 18 is covered by a crust 22
which consists essentially of frozen electrolyte constituents and
additional alumina. As alumina is consumed in the electrolyte 18,
the frozen crust is broken by a suitable crust breaker, not shown,
and more alumina fed into the electrolyte by the opening of ore
valve 24 which causes the alumina to be fed from the feed hopper
26. The anode is connected by anode bus bar 28 to the positive pole
of a source of supply of electrolyzing current. For purposes of
completing the electric circuit, use is made of cathodic
current-conducting elements or collector bars 30. The collector
bars 30 extend through suitable openings provided in the metal
shell and insulation layer with the inner ends thereof projecting
into the cell lining. The outer ends of the element are connected
by suitable means to the other side of the supply line.
As shown in FIG. 1, the cells are connected in series over a
suitable DC current-sensing device or transducer or ammeter (I) 34
to a suitable power supply, one side of the supply being fed to the
anode system of the first cell and the cathode of the first cell
being in turn connected to the anode of the second cell, etc., the
cathode of the last cell being connected to the other side of the
supply line. One such sensing device is that known in the trade as
the Dyn/Amp DC-metering system. The cells also include suitable
means for raising and lowering anodes 20 such as an air motor
controlled by solenoid valves 36, a suitable crust breaker device
(not shown) for each cell and the alumina ore drop previously
discussed with the ore valves being operated in a suitable manner
such as air operated through solenoid valves. A suitable volt meter
or DC voltage isolation amplifier 38 is connected between the anode
and cathode of an associated cell to provide an indication of the
voltage drop across the cell. A suitable computer 40 is connected
into the system, or more desirably, to minimize wiring cost,
selector relays 52 are connected between the computer and the
system as shown in the figure. Also operably connected to the
computer 40 are operator's panels 44, tape punch 46, tape reader 48
and typewriters 50.
The process control program (system) may be generally described as
a plurality of functional programs and subprograms used for
monitoring, supervising and optimizing potline control. In the
process scanning program which in one embodiment is scheduled to
run at predetermined time intervals, the computer sequentially
samples the cell voltage of all cells in the potline as provided by
the isolation amplifier 38 and the line amperage as provided by the
current sensing device 34. The optimum back EMF value determined in
a separate background program is used in the calculation by the
computer of a smoothed resistance from several sequential
measurements. A separate control program updates the base level
resistance and looks for deviations of the smoothed resistance from
the base level in excess of an assigned limit. If the computer, in
its scan of the readouts, detects that the smoothed resistance
differs from the base level by more than an assigned limit a
special subprogram is entered immediately and control of the
particular pot which is detected to be approaching the threshold is
affected by signals from the computer over the crust breaker
conductor to the detected cell to break the crust and signals over
the "alumina ore drop" conductors to the ore valve 24 in the
detected cell to increase the alumina concentration in the molten
bath. The electrolysis in the cell then continues its normal course
until the cell is once more detected as approaching the
predetermined threshold.
Tests were run over a period of several months in a conventional
prebake anode cell of the type shown in FIG. 1. This was a
commercial size cell which was operated at a normal amperage in the
neighborhood of 90,000 amps and at a normal voltage drop of about
4.5 volts. The value of back EMF which provided the optimum output
was predetermined to be about 1.5 volts. FIG. 2 is a portion of the
cell resistance graph produced during these tests. The voltage drop
across the cell and the current to the cell were measured every 5
seconds and process values were smoothed over six such
measurements. A computer of the type indicated above was used to do
this. Since feeding alumina to the cell upsets the cell resistance
and since it is desirable to set the cell resistance by controlling
the voltage, 5 minutes were set aside after each feeding of alumina
to the cell as a stabilizing period for the voltage and the
resistance. This allowed the alumina fed to the cell to dissolve
into the electrolyte and the voltage to be adjusted as necessary (A
in FIG. 2). When the cell resistance had stabilized a smoothed
resistance level was calculated for a 5 minute period. This long
term smoothed resistance became the base level for control decision
purposes (B in FIG. 2).
Although the cell resistance normally increases gradually from this
point on, it might also decrease at first and rise again. If it has
a tendency to decrease this indicates that more than 4 percent
alumina by weight is dissolved in the electrolyte. Hence, it is
desirable to consume this excess alumina in the reactions resulting
in the production of aluminum. This has a further undesirable
characteristic in that it tends to delay the anode effect warning
period if the base or set point resistance level is not readjusted
downward. To correct this situation, a new smoothed resistance was
recalculated every 5 minutes (C & D on FIG. 2); and if its
value was lower than the previous set point, it became the upgraded
base level.
A smoothed resistance was calculated every 30 seconds using the six
scan average resistance. This allowed smoothing of the random
variations in the resistance curve and also made the detection of
the critical point easier. The critical or control decision point
(E in FIG. 2) was reached when the smoothed resistance curve
exceeded the current base resistance level by more than an assigned
limit. When this occurred, a controlled amount of additional
alumina was fed to the cell and the cycle restarted. As can be seen
in FIG. 2, the target resistance was approximately 30.2 micro ohms
and the base resistance level was approximately 30.14 micro ohms.
The assigned limit was 0.3 micro ohms.
With this setup the control decision point was reached when the
alumina concentration had lowered to about 2 to 21/2 percent and 1
percent of alumina was added so as to increase the concentration to
about 3 to 31/2 percent. At stable operation, a control decision
point was usually reached every 20 to 25 minutes.
This process worked very well in practice. The average alumina
concentration during the test period was 3.1 percent and the anode
effect frequency was reduced drastically and excellent voltage
control was achieved.
While there has been shown and described hereinabove, possible
embodiments of this invention, it is to be understood that the
invention is not limited thereto and that various changes,
alterations, and modifications can be made thereto without
departing from the spirit and scope thereof as defined in the
appended claims wherein:
* * * * *