A fully integrated process is provided for the recovery of valuable
components from waste materials generated in electrolytic aluminum
reduction systems. The waste materials, such as spent pot linings, channel
and trench cleanings, floor sweepings and spent alumina from offgas
purifying dry scrubbers, are combined, then pyrohydrolyzed at elevated
temperature. Fluoridic values, such as NaF and HF can be recovered from
the offgas generated by pyrohydrolysis, while alumina and Na.sub.2 O
values, or if desired, sodium aluminate, is reclaimed from the solid
residue of pyrohydrolysis.
The fluoridic values from the pyrohydrolysis offgas can be used for the
manufacture of both electrolytes for aluminum reduction cells and also for
the production of anhydrous HF. The alumina from the pyrohydrolysis
residue can be reclaimed by a Bayer process-type leach with a caustic
solution and the recovered high purity alumina utilized, for example, as
reduction cell feed and/or for scrubbing reduction cell offgases. If the
solid residue of pyrohydrolysis contains significant amounts of sodium
aluminate, this material can either be directly used for dry scrubbing
cell offgases, or if desired, utilized for production of high purity
alumina. SU
BACKGROUND OF THE INVENTION
This invention relates to a fully integrated system for the recovery of
valuable components from spent materials generated in the electrolytic
reduction of alumina to metallic aluminum with simultaneous improvement in
the purity of aluminum produced in the reduction process.
In the production of metallic aluminum by electrolysis of reduction-grade
Al.sub.2 O.sub.3, the electrolysis is generally carried out in reduction
cells or pot lines which are lined with a carbonaceous material. During
the life of the cells, this carbon lining is gradually destroyed by
penetration of bath materials into the lining, for example, metallic
aluminum, cryolite and alumina. Also, due to the high temperatures
employed in the electrolytic reduction process, gradual aging of the
carbonaceous lining takes place. The combined result of penetration and
aging can reach a stage where the further operation of the cell or cells
reaches an economically prohibitive point and replacement of the
carbonaceous lining becomes a must. The unusable or "spent" potlining is
then removed and in most instances stockpiled. In large aluminum reduction
facilities, this lining replacement is a continuous process and,
consequently, the quantity of spent lining stockpiled increases from day
to day.
In aluminum reduction facilities, where metallic aluminum is produced by
the electrolysis of Al.sub.2 O.sub.3 in the presence of a fluoridic
electrolyte, such as cryolite (Na.sub.3 AlF.sub.6), the electrolysis
results in offgases of high fluoride content. In addition to the fluoride
content, the offgases generated in the reduction process contain gaseous
and particulate impurities, for example, volatilized metallic compounds
and carbon derivatives, together with solid matter and nonvolatile
carbonaceous materials. The quantity of volatilized and solid carbon
compounds in the offgases vary within wide limits depending on the type of
anode used in the reduction system. Soderberg carbon anodes generate far
more of these materials than prebaked carbon anodes.
In order to protect the environment and to provide healthy operating
conditions in the reduction facility, these offgases must undergo a
purification process for the removal of harmful constituents. A common
process for cleaning the offgases is to subject them to a dry scrubbing
treatment which effectively removes essentially all of the environmentally
harmful impurities from the offgases. In the dry scrubbing treatment of
reduction offgases, alumina is usually employed as the scrubbing medium.
The alumina readily absorbs the fluoridic components of the offgases and
also captures the particulate impurities. It further removes harmful high
molecular weight carbon derivatives. Consequently, the dry scrubbing of
reduction cell offgases with alumina is an effective purification process
resulting in purified off-gases containing only environmentally harmless
components.
While scrubbing of the offgases solves the environmental and health
problems, it poses a serious disposal problem. The spent alumina from the
scrubber system is heavily laden with impurities and cannot be directly
employed as feed for reduction cells without introducing unacceptable
alloying components in the metal to be produced and without seriously
interfering with the efficient operation of the reduction cells. Since the
alumina is spent, it cannot be used for further scrubbing without
purification.
In the production of metallic aluminum by the electrolytic reduction of
Al.sub.2 O.sub.3 in a series of cells, a significant quantity of impure
metal and contaminated aluminum oxide feed are also generated in the form
of floor sweepings, channel and trench cleanings. These materials, due to
their high impurity content, cannot be directly employed for making
metallic aluminum of commercial purity and, in general, if not blended
with pure feed materials, are considered as waste with no convenient way
of disposal.
Thus, from the above, it becomes clear that the producers of aluminum by
the electrolytic process have major problems relative to the disposal of
spent potlinings, exhausted alumina from the dry scrubbers, floor
sweepings, channel and trench cleanings. These problems have been acutely
recognized by operators of aluminum reduction facilities all over the
world and partial solutions have been offered to overcome one or more of
the problems associated with the generation of these spent materials.
Several proposals have already been made to deal with the problems
resulting from the accumulation of excessively large quantities of spent
potlinings.
Thus, in U.S. Pat. No. 3,151,934, it has been suggested that the spent
potlinings be crushed, followed by extraction of fluoridic values and
dissolution of metallic aluminum with a sodium hydroxide solution. The
alkaline extract, after carbonation, is utilized for the preparation of
synthetic cryolite, while the essentially fluoride-free carbon residue, is
again contacted with an NaOH--Ca(OH).sub.2 solution. This treatment of the
carbon residue or "black mud" removes any lithium present and then the
black mud residue is disposed of. The treatment disclosed in this
reference results in only a partial and expensive solution of the disposal
problem; large quantities of black mud remain after the extraction
treatments which cannot be utilized for any forseeable purpose.
In U.S. Pat. No. 3,606,176, it has been suggested to crush the spent lining
of reduction cells, followed by removal of the metallic aluminium content
by mechanical screening. The residual crushed carbonaceous lining is then
further reduced in size and subsequently slurried with salt water to allow
separation of the bulk of the carbon fraction by flotation from cryolite,
alumina and residual aluminum. Again, the carbon fraction is discarded and
since this is the major portion of the spent lining, stockpiling with the
corresponding problems has not been solved.
Another process for treating spent potlinings is presented in U.S. Pat. No.
3,635,408. According to this reference, spent carbon lining is crushed,
then treated with dry steam at a temperature insufficient to destroy the
carbon. The steamed, carbonaceous material is then classified into coarse
and fine fractions. The fine fraction is subjected to a chemical treatment
for the recovery of its fluoridic values, together with the alumina and
aluminum content, while the coarse fraction is utilizable for making new
cell linings. However, if the coarse fraction resulted from cell linings
of the monolithic type, the coarse fraction has an approximate carbon
content of only 53%, the balance being fluorides, alumina and aluminum.
This relatively high percentage of impurity content, when the coarse
fraction is used directly for making of new cell linings, will adversely
affect the electrical and mechanical properties of the new cell lining
and, consequently, will provide lower life expectancy, coupled with
operating efficiencies below the desired parameters. If the coarse
fraction results from spent linings made of the prebake type, the carbon
content is higher and the undesirable impurity content is lower. However,
the new linings made from this material will still perform below the
desired values in terms of efficiency and life.
Thus, it can be observed that although many efforts have been made to
utilize the spent linings of reduction cells, these efforts only provided
partial solutions to the existing problems which the ever-increasing piles
of spent potlinings further emphasize.
Regarding the spent alumina recovered from the dry scrubber systems,
several processes have already been recommended for the treatment of this
impurity-laden material. For example, German Pat. No. 970,919 (granted
Nov. 13, 1958) has recommended the calcination of the spent alumina
removed from the scrubber system. Calcination of this alumina in the
presence of sodium carbonate below the sintering temperature of cryolite
results in cryolite which can be recycled to the reduction cells as
electrolyte. This cryolite would be a suitable substitute for either
natural or synthetic cryolite generally employed for this purpose if it
would be free of metallic impurities. However, the calcination employed to
convert the spent alumina to cryolite can only remove some of the
volatilizable impurities and perhaps carbon. It does not eliminate the
metallic impurities, such as iron, silicon and phosphorus, and,
consequently, by recycling it directly to the cell, the undesired impurity
content in the produced metallic aluminum will constantly increase. This
increase in impurity level significantly lowers the commercial value of
the produced aluminum, apart from the deleterious effects caused by these
impurities with regard to the cell lining life and efficiency of the
electrolytic reduction process.
More currently, it has been suggested in U.S. Pat. No. 4,006,066, that the
spent alumina from dry scrubbers, which are appended to the electrolytic
aluminum reduction cell system, can be purified by classifying the
impurity-laden alumina to coarse and fine particle size fractions. The
reason for this size separation is the fact that the major quantity of
impurity from the reduction cell offgas is captured by the fine fraction
of the alumina employed in the scrubber system. The coarse fraction will
also capture impurities from the offgas; however, the impurity content of
the coarse fraction is significantly smaller in proportion to its weight.
Consequently, separation by size affords a preliminary purification and
allows the return of the coarse fraction directly to the reduction cell as
partial feed and also as partial fluoridic electrolyte replacement. This
recycling of the coarse fraction, which can amount to up to about 80-85%
of the alumina from the scrubber system, greatly assists in reducing the
quantity of alumina to be purified before further utilization. The
impurity content of this coarse fraction nevertheless still causes similar
problems as described hereinbefore.
The fine fraction from the classification contains the major amount of the
impurities from the reduction cell offgases and this fraction, while
smaller in percentage by weight than the coarse fraction, still presents a
large quantity to be dealt with. The aforesaid U.S. reference
pyrohydrolyzes this fine fraction in a special rotary kiln with water
vapor and the resulting alumina product, which is free of fluorine, but
still contains the other impurities as stated, is usable, for example, in
the ceramic industry. This alumina, due to its high impurity content,
cannot be returned to the electrolytic aluminum production system.
Consequently, it constitutes a significant loss and affects the overall
economy of aluminum production.
Even more recently, in copending U.S. pat. application Ser. No. 709,025
(filed July 27, 1976), a process has been described which allows the
separation of essentially all of the impurities from the spent alumina
recovered from the dry scrubbers of aluminum reduction cell offgases. This
is accomplished by slurrying the spent alumina with a solvent, followed by
an ultrasonic treatment of the slurry. Although the ultrasonically
treated, highly pure alumina can be recycled to the scrubber system or the
cells after drying, the process, due to the large quantities of spent
alumina to be treated, can create logistics problems and equipment
constraints.
Channel and trench cleanings and floor sweepings found in aluminum
reduction facilities can contain a large percentage of metallic aluminum,
together with cryolitic flux and aluminum oxide. Recovery of the aluminum
values can be accomplished by screening or melting these materials in a
furnace in the presence of a suitable flux. This operation requires
special equipment and chemicals, not to mention the significant input of
energy. This type of purification allows the recovery of metallic
aluminum; however, both the cryolite and the alumina values become lost
and in addition, the process poses disposal problems.
From the above, it can be observed that there is a need for an integrated
system which is capable of dealing with all of these spent materials with
simultaneous recovery of all of the valuable components from these
by-products of the electrolytic aluminum reduction process. The integrated
system described hereinafter provides such a solution whereby all of the
above-described spent materials can be fully utilized without affecting
the purity of the metallic aluminum produced in the electrolytic reduction
cells.
BRIEF SUMMARY OF THE INVENTION
An integrated process is provided for the recovery of valuable components
from aluminum, carbon and fluoride-containing waste materials generated in
electrolytic aluminum reduction systems. From these waste materials, which
include spent potlining, spent alumina from dry scrubbers used for
reduction cell offgas purification, channel and trench cleanings and floor
sweepings, a feed is prepared for a pyrohydrolysis unit. Preparation may
include comminution to less than about 6 mm particle size if the waste
material is of greater size. If there are fine particles below about 1-2
mm in size, these are advantageously shaped prior to pyrohydrolysis. Also,
if desired, sufficient carbon can be added to the feed to provide
self-sustaining combustion in the pyrohydrolysis unit. Pyrohydrolysis of
the feed is accomplished at about 1100.degree. to 1350.degree. C., while
sufficient water is introduced into the pyrohydrolysis unit to obtain an
offgas containing the fluoridic values from the feed. The offgas, after
cooling, may be sequentially utilized for the production of NaF or an
NaF-enriched alumina in controlled amount. Then either an AlF.sub.3
-enriched alumina or an HF solution is made. The solid clinker resulting
from pyrohydrolysis is utilized for the production of high purity alumina
and recovery of Na.sub.2 O values by treating it according to the Bayer
process. If desired, sufficient basic sodium salts, such as Na.sub.2
CO.sub.3 and/or NaOH, is added to the feed or the hot clinker. In this
instance, the clinker recovered from the pyrohydrolysis unit will contain
a major amount of sodium aluminate. This sodium aluminate can either be
used for the production of alumina or employed in dry scrubbers for the
capture of impurities emanating from reduction cells. If desired, the
sodium aluminate can be used for both of these purposes.