D I bureau of mines 5781

n report of investigations
USING MOLTEN ZINC TO EXTRACT
ALUMINUM FROM ALUMINUM-SILICON
ALLOYS: A PROGRESS REPORT
By H. S. Caldwell, Ir., and M. I. Spendlove
UNITED STATES DEPARTMENT OF THE INTERIOR
BUREAU OF MINES
(1961)
Burea.u of Mines
of
USING MOLTEN
H. S.
3
TO EXTRACT ALUMINUM FROM ALUMINUM-SILICON
ALLOYS: A PROGRESS REPORT
by
, Jr. and M. J. Spendlove
ERRATA
Should rea.d in part
from the lower vessel (4) and
condensed to the liquid state in
the upper vessel (2). The liquid
zinc is refluxed into the lower
vessel (
5
5, first by
block (1).
the water-cooled
USING MOLTEN ZINC TO EXTRACT
ALUMINUM FROM ALUMINUM-SILICON
ALLOYS: A PROGRESS REPORT
By H. S. Caldwell, Jr., and M. J. Spendlove
reporl of investigations 5781
UNITED STATES DEPARTMENT OF THE INTERIOR
Stewart L. Udall, Secretary
BUREAU OF MINES
Marling J. Ankeny, Director
This publication has been cataloged as follows:
Caldwell, Herbert S
Using molten zinc to extract aluminum from aluminum-silicon
alloys: a progress report, by H. S. Caldwell, Jr., and M. J.
Spendlove. [Washington] U. S. Dept. of the Interior, Bureau
of Mines [1961J
15 p. illus., rabies. 27 em. (U. S. Bureau of Mines. Report of
investigations, 5781)
Bihliographieal footnotes.
1. Aluminum. 2. Aluminum-silicon alloys. 3. Zinc-Metallurgy. I.
Spendlove, Max J joint author. I. Title: Molten zinc to extracr
aluminum. (Series)
[TN23.U7 no. 578J.] 622.06173
U. S. Dept. of the Int. Library
CONTENTS
Surnrnary " " , Iff " " It " Iff " " " " " Iff II , " "
Introduction ..................
Aluminum extraction process ........................
Application of extraction process, procedure and results
Crude alloy feed ....
Induction-heated unit .. " .. """""""".",,.,,"" """""."""
Electrical-resistance-heated unit .
Gas .... fired unit .. ".""",,. ".,.""""""".. """""""""
Study of process conditions.
Pressure .
Leaching .
Conclusions ..
Future research.
1.
2.
3.
4.
5.
6.
1.
2
3
4.
5
6
7.
ILLUSTRATIONS
Fundamentals of aluminum extraction.
Diffusion of zinc into AI-Si alloy,.
Induction-heated unit ...
Extraction of aluminum from AI-Si alloy ...
Electrical-resistance-heated unit ....
Gas-fired unit."""""".,,""""""""",,.
TABLES
Extraction experiments, induction-heated unit ..
Extraction experiments, gas-fired unit
Effect of pressure on dissolution of aluminum .
Liquid-zinc leaching" .. "",,"""""" III " " " " " " " II " " " " " " " "
Zinc-vapor leaching" .. ",,"""""" II " " .. " " " Iff " " ill II " .. "" " " " 0 ". " ..
Effect of alloy particle size on leaching
Effect of AI-Si alloy iron content on aluminum
ext rae tion" " " " " " ., " " " II " " " " " " " " " " " " , " " " " .. " III " ......
1
1
3
5
5
5
7
9
11
11
12
15
15
3
4
6
7
8
10
6
11
12
13
13
14
14
USING MOLTEN ZINC TO EXTRACT ALUMINUM
FROM ALUMINUM-SILICON ALLOYS:
A PROGRESS REPORT.Y
by
H. S. Caldwell, Jr.V and M. J. SpendloveV
SUMMARY
Molten zinc, condensed from zinc vapor, was used by the Federal Bureau of
Mines to leach aluminum from an aluminum-silicon alloy made by carbo thermic re-
duction of silicious aluminum ores. Zinc requirements were minimized by re-
fluxing condensed zinc in a low-pressure, Soxhlet-type distillation unit. The
minimum ratio of zinc used to aluminum in the crude alloy was approximately
2:1. When the system pressure was reduced from atmospheric pressure to 100
microns or less, the rate of aluminum extraction increased by a factor of 20.
Leaching rates were much higher when the zinc vapor was condensed directly on
the crude alloy than when molten zinc was passed over the alloy in the absence
of appreciable zinc vapors.
Observations indicated higher extraction efficiencies from crude alloys
containing greater amounts of iron. Complete extraction was obtained with
negligible loss of zinc.
Assuming complete removal of zinc, the aluminum products will contain 1
to 6 percent silicon and about 0.5 percent iron plus titanium. The leached
crude-alloy residue is a highly friable spongelike material containing about
80 percent silicon, several percent iron and titanium, with the remainder
aluminum.
This extraction method has been patented (Patent 2,810,637) and assigned
to the Government. Research and development investigations are continuing at
the College Park Metallurgy Research Center.
INTRODUCTION
Although aluminum is the most abundant metal in the earth's crust, baux-
ite is the only ore used commercially for producing aluminum. Ordinarily,
only ores containing more than 45 percent alumina and less than 15 percent
silica are considered commercially valuable.
II Work on manuscript completed November 1960.
II Metallurgist, Metallurgy Research Center, Bureau of Mines, College Park,
Md.
2
Because the domestic reserve of high-grade bauxite are is relatively
meager, considerable research has been directed towards developing methods
for producing aluminum freml low-grade bauxite, clay, anorthosite, and other
abundant raw materials that cannot be processed by present commercial methods.
One pertinent project, conducted at the Tennessee Valley Authority labo-
ratories in 1947, was devoted to the production of an aluminum-silicon alloy
by electrothermal reduction of clay with coke.11 More recently, the Bureau
of Mines, in cooperation with the Apex Smelting Co. of Chicago, developed
significant improvements in this process during electric-smelting experiments
on calcined clay, silica, and
The crude AI-Si alloy produced in this reduction is a bright, large-
grained, brittle material containing 30 to 60 percent aluminum, 30 to 50 per-
cent silicon, and a few percent iron and titanium. A similar alloy produced
in Europe by this method is reported to be used as a deoxidizing agent in
steelmaking and in the production of "silumin" casting alloys. Two commer-
cially important binary alloys of aluminum and silicon, No. 43 and No. 13,
each contain 12 percent silicon. Alloy 43 is used in producing sand and
permanent mold castings, and alloy 13 is widely used in diecasting. There
are no known commercial processes in which the alloy is used as a starting
material for producing a marketable grade of aluminum metal.
Methods for separating aluminum from Al-Si alloys have been suggested
by other The most prominent of these proposals is the
Loevenstein in which molten AI-Si alloy is cooled to the eutectic
temperature of 577
0
C. and the aluminum-rich liquid phase, containing 11.7
percent Silicon, is filtered off. Further refining is achieved by adding
zinc to the filtrate to form a eutectic having a melting point of 382
0
C.
Additional silicon is filtered from the zinc-aluminum at this temperature
to form an alloy containing only minor amounts of silicon. Differences in
the volatility of aluminum and zinc permit the refining of the aluminum prod-
uct by evaporating the zinc. The Zn-Al eutectic at 382
0
C. contains about
95 percent zinc, all of which must be evaporated to obtain refined aluminum.
11 Striplin, M. M., Jr" and Kelley, W. M., Aluminum-Silicon Alloys by
Electrothermal Reduction of Clay With Coke: Chem. Eng. Prog., vol. 43,
1947, pp. 569-578.
Rasmussen, R. T. C., Electric Smelting at the Bureau of Mines Seeks Utili-
zation of Northwest Ores: Jour. Metals, vol. 4, No. 12, December 1952,
pp. 1276-1277.
Banning, L. H., and Hergert, W. V., Experimental Production of Al-Si
Alloys in a 3-PhaseFurnace: Jour. Metals, vol. 7, No, 5, May 1955,
pp. 630-633.
Fursman, Oliver C., and Banning, Lloyd R., Experimental Smelting of
Aluminum Silicates to Produce Aluminum-Silicon Alloys: Bureau of Mines
Rept. of Investigations 5575, 1960, 23 pp.
il Hayakawa, Y., The Steam Process and Its Mechanisms: Jour. Electrochemical
Assoc. (Japan), No. 16, 1948, pp. 37-42.
Loevenstein, H., Process for Manufacturing of Aluminum: U.S. Patent
2,198,673, Apr. 30, 1940.
2
\
1---
\
/ / ~
\
/ I-=-
\
/ I
\
/ f
\
/
\
I
\
I
I I
I
I
I
I
I
I
I
I
I
I
\
I
I
x
\
I
I
x
/
x
4 x
\
I
x- x - x - x
- x - x -- x --
-- )( -
I Cooling block
2 Condenser
3 AI-Si column
4 Zinc evaporator
x Aluminum
o Silicon
- - Zinc
3
The aluminum-extraction ap-
paratus and process described in
this report were designed to
eliminate the need for very large
quantities of zinc and to reduce
the separate dissolution, filter-
ing, and distillation steps to
manipulative phases of one opera-
tion. It was proposed to perform
the operation at reduced pressure
for higher rates of zinc vapori-
zation at low operating tempera-
tures.
The specific objectives of
the investigation were:
1. To obtain relatively
pure aluminum from alwninum-
silicon alloys.
2. To design, construct,
and test gas and electrically-
heated extraction units.
3. To develop leaching
techniques that require a mini-
mum of zinc and retain the ad-
vantages of zinc as a leaching
agent.
4. To determine optimum
temperature, time, pressure,
particle size, and alloy compo-
sition for maximum extraction
efficiency.
ALUMINUM EXTRACTION PROCESS
The fundamentals of the ex-
traction process are illustrated
j
in fig. 1. Zinc is volatilized
(
from tha lower vessel (3) and
c ~ n d e n s e d to the liquid state in
the upper vessel (1). The liquid
~ zinc is refluxed into the lower
~ vessel (2), which contains a
charge of crushed Al-Si alloy.
Aluminum is selectively leached
from the crude alloy by the
molten zinc and returns with FIGURE 1_ - Fundamentals of Aluminum Extraction.
4
AI-Si alloy; X100, Etch, 0.5 percent HF,
20 seconds.
Zinc completely diffused into AI-Si alloy;
X 100, Etch, 0.5 percent HF, 20 seconds.
Zinc partly diffused into AI-Si alloy; X100,
Etch, 0.5 percent HF, 20 seconds.
Si Sponge, AI and Zn removed; X20.
FIGURE 2. - Diffusion of Zinc Into AI-Si Alloy.
5
the zinc to the lower vessel as an aluminum-saturated zinc alloy. Relatively
little zinc is required by this technique because zinc can be vaporized readily )\
from the aluminum and recycled through the Al-Si alloy many times during the j
extraction operation. After a specified leaching period the upper vessel is ~ ~
cooled below the\melting point of zinc by lowering the water-cooled block (4) . ~ \
The zinc vapors are then condensed to the solid state and retained in the ----- j
upper vessel. Refined aluminum is left in the lower vessel, and a bed of ~
porous silicon and other impurities remains in the leaching vessel.
Photomicrographs of the various stages of the leaching process are shown
in figure 2. View ~ shows the microstructure of the Al-Si alloy before leach-
ing. The large plates and bars are silicon crystals formed when the molten
Al-Si alloy was slowly solidified. The area surrounding these large crystals
is a mixture of Al-Si corresponding closely to the eutectic composition, 88.3
percent aluminum and 11.7 percent silicon.
View B shows a section partly leached with zinc. The dark area at the
bottom right is where zinc has diffused into the crude alloy. The extent of
diffusion is clearly marked by the sharp boundary between the dark and light
area. The microstructure of the alloy after a period of complete leaching is
shown in view f. The silicon crystals appear to dissolve more slowly than the
Al-Si eutectic mixture. The areas about the plates are small channels of Zn-
Al alloy. The porosity of the silicon sponge after removal of zinc and alumi-
num is shown in the photomacrograph, view D.
APPLICATION OF EXTRACTION PROCESS, PROCEDURE AND RESULTS
Crude Alloy Feed
The same crude alloy was used in all tests except those in which the
effect of variations in iron content was studied. Analysis of the alloy re-
vealed the following percentages: Al, 47; Si, 42; Fe, 6.5; and Ti, 4.5.
Induction-Heated Unit
The unit used in the initial phase of the experiment is described in
figure 3. Heat is supplied to the unit by a high-frequency induction coil
(17) which is inductively coupled to a carbon crucible (7). A hollow, quartz
cylinder (22) provides a vacuum-tight enclosure for the various other carbon
vessels shown. Crushed Al-Si alloy is placed in a circular trough like vessel
(2), which has an axial opening for conducting the zinc vapor from the evapo-
ration crucible (la). High rates of zinc evaporation were obtained at rela-
tively low distillation temperatures by reducing the system pressure below
100 microns. Samples for analysis were obtained at the end of each time
interval by shutting off the furnace and allowing it to cool to room tempera-
ture before opening it.
Results of typical extraction experiments with the induction-heated unit
are presented in table 1. The composition of the recovered aluminum was cal-
culated on the basis of 100 percent removal of zinc.
6
5
(J-- {;j -=<J-
I II
18 / 1
I
I I I , , ~ ~
/0 Carbon -evaporation crucible
Ib Carbon-condensing crucible
2 Crude-alloy container
3 Carbon-cooling cylinder
4 Water jacket
5 Cooling-cylinder adjustment
6 Vacuum slipjoint
7 Induction-furnace crucible
8 Insulation
9 I nsulating brick
/0 Carbon spacer
/ I Thermocouple well
/2 Thermocouple channel
/3 Rubber stopper
/4 Water-cooling tubes
/5 Pressure-distribution ring
/6 Adjustment nuts
/7 Induction coil
/8 Induction-furnace housing
/9 Vacuum line
20 Vacuum head
2/ Rubber gasKet
22 Quartz cylinder
o 4 8 12 16 20
Scale, inches
FIGURE 3. - Induction-Heated Unit.
TABLE 1. - Extraction experiments
l
induction-heated unit
Leach Aluminum Total Composition of
Test Zn-A1 temper- Leach avai1- Aluminum aluminum product,
No. ratio ature, period, able, extracted, extracted, percent
cC.
minutes grams grams percent Al Si Fe Ti
1 10.84 500 0-105 172.0 50.9 29.6 97.2 1.6 0.6 0.6
105-165 138.4 30.1 47.0 96.8 2.5 .4 .4
165-225 105.3 19.9 58.5 96.9 2.0 .7 .4
2 9.39 560 0-120 1,341. 0 537.2 40.1 97.8 1.1 .2 .9
120-240 803.8 419.3 71.3 96.9 2.4 .2 .5
240-360 384.5 238.7 89.1 96.4 3.0 .2 .4
3 2.26 580 0-240 990 862.2 87.1 93.8 5.4 Fe+Ti -Y.8
240-480 127.9 127.9 100.0 93.5 5.8 Fe+Ti 1.1.7
1./ Estimated.
7
Test 1 in the table shows approximately 60 percent of the aluminum ex-
tracted after a leaching period of 225 minutes. The aluminum content of the
product after removal of zinc was 96.9
Test 2 shows about 90 percent of the
uct 96.4 aluminum and 3.0
recovered as a final prod-
silicon.
In test 3, a 100-percent aluminum extraction was achieved, but the
nurn 5.8 percent silicon. A very low zinc-to-aluminum ratio .26:1)
was used in this test. Although 100-percent aluminum extraction was achieved,
the final product contained a perc of impurities due primarily to a
higher leaching temperature and a longer leaching period.
Calculated rates of aluminum extraction for these tests are illustrated
in 4. The rate increased with increasing leaching temperature,
silicon contamination also increased from 2 to 3 percent between tests 1 and 2
and from 3 to 6 percent between tests 2 3.

c:
Q)
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o
w
f-
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0::
f-
X
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::2:

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::2:

-l

-'

f-
0
f-

40
20
60 120 180 240
TIME, minutes
300 360
FrGURE 4. - Extraction of AI num From AI-Si AI loy.

420 480
An electrical-resistance furnace was constructed to include the features
shown in figure 5. The 24- by 20- by 7-inch, box-shaped evaporator (8) was
made large and shallow to provide a maximum evaporation area with a minimum
8
6
LEGEND
_ Steel
n::::::l Graphite
~ Insulating brick
IlII1Ill Rubber
Cooling coils
o Heating elements
2
.

o 2 4 6 8
-- -- Scale, inches
2
3
4
5
6
T
8
9
10
/I
12
II
Condenser adjustment
Water-cooled jacket
Condenser sleeve
Condenser
Leaching column
Thermocouple wells
Alloyreturn conduit
Evaporator
Vacuum port
Vapor conduit
Vacuum-tight enclosure
Collector plate
FIGURE 5_ - Electrical-Resistance-Heated Unit.
6
of zinc. The condenser (4) was an inverted cup-shaped vessel that could be
raised or lowered inside of a water-cooled metal jacket (2). The zinc vapor
passed from the evaporator through a heated conduit (10) to the top of the
10-inch-diameter leaching column (5). Zinc vapor was condensed to the liquid
state in the condenser and refluxed into the bed of Al-Si alloy below. Alu-
minum was leached from the alloy as the zinc passed through the alloy bed.
The Al-Zn alloy was collected in the annular recesses of a removable collector
plate (12) and transferred through the return line (7) into the evaporator. A
9
liquid-metal trap was provided in the return line to prevent eroded silicon
particles from becoming mechanically entrapped in the Zn-Al alloy and carried
into the evaporator. The floor of the evaporator was elevated at the entrance
so that the molten Zn-Al flowed some distance over the heated floor be-
fore it reached the main of molten metal. The turbulence caused in the
metal this action provided more metal surface for evaporation and reduced
the tendency for aluminum to concentrate at the evaporating surface as the
alloy became depleted of zinc. Separate heating elements were provided for
the various compartments. elements were not installed about the
leaching column (5), since it was believed that a little heat would be needed
in this area to compensate for conduction and radiation losses. The principal
advantages of this unit over the induction-heated unit are: (1) Greater evap-
oration area in proportion to the amount of zinc, (2) greater available volume
in the extraction vessel, and (3) easier removal of products.
Several unforeseen characteristics were observed when the
unit was put in operation. The erature of the leaching column continued
to rise for some time after the heat had been turned off and external cooling
had been applied. Also, the condenser cooling capacity was far less than ex-
pected because the actual heat conduction from the graphite condenser to the
cooling jacket was lower than estimated. However, tests were continued since
the work schedule did not extensive modification of the unit.
The results for a typical operation follow:
The evaporator was stabilized at 580
0
C. Under these conditions, the
condenser temperature stabilized at 458
0
C. and the leaching column era-
ture at 455
0
C. The test was run for 8 hours; this period 48.1 percent
of the aluwinum was extracted. The final product showed 98.4 percent aluminum,
1.5 silicon, and less than 0.2 percent iron plus titanium. Although
this recovery was lower than that for the induction-heated unit, the quality
of the aluminum extracted was ly improved.
The observed rate of zinc was considerably less than the
theoretical maximum rate corresponding to the temperature and surface area
of the evaporator. Factors contributing to the low recovery were: (1) Zinc
was not being evaporated from a pure zinc bath, and (2) the failure of the
small zinc-vapor conduit leading into the leaching column to permit free
escape of zinc vapors from the evaporation crucible.
The NichromeZl electrical heating elements showed appreciable deteriora-
tion after 50 hours of operation under vacuum.
Gas-Fired Unit
Neither of the electrical units to offer promis
possibilities for practical application because of the high cost per unit of
7/ Reference to specific makes or models of equipment is made to facilitate
understanding and does not imply indorsement of such devices by the
Bureau of Mines.
10
/0
o 2 4 6 8 10 12
Scale, inches
/ Furnace insulation 6 Condenser
2 Evaporator T Vacuum line
3 Vapor conduit 8 Leaching column
4 Cooling coil 9 Alloy-return conduit
5 Thermocouple well /0 Water-cooled end plate
/ / Combustion chamber
FIGURE 6_ - Gas-Fired Unit.
/0
heat and the rela-
tive difficulty in
conducting it into
a vacuum. A gas-
fired unit was con-
structed to examine
the problems in
this type of heat-
ing. Thea e per-
tained primarily to
furnace design and
construction mate-
rials. Materials
with high thermal
conductivity and
corrosion resist-
ance were required,
and the design
would have to pro-
vide optimum condi-
tions for the proc-
ess. Features of
the gas-fired ex-
traction apparatus
are shown in fig-
ure 6. The zinc
evaporation cham-
ber (2) is posi-
tioned horlz-ontally
below the vertical
leaching column (8).
The purpose is to
expose a maximum
surface area of
mol ten zinc for
maximum rates of
evaporation. The
zinc-evaporator
section consists
of an outside shell
of stainless steel,
29 inches long,
with a l/4-inch
wall thickness and
a 4-1/2-inch inside
diameter. A graph-
ite inner liner is
used as the cruci-
ble to retain 30 pounds of zinc charge and protect the shell from attack by
the zinc.
Zinc vapors are conveyed from the evaporation crucible to the condenser
through a 4-inch-inside-diameter, graphite-lined stainless steel pipe (3),
The condenser (6) is a water-cooled iron cylinder closed at the bottom and
protected on the furnace side by a graphite sleeve. The condenser extends
into the leaching section so that the flanged, open end engages a mating
flange on the leaching column. A rubber gasket is used to make a vacuum-
tight seal. The condensing temperature is controlled by varying the rate of
circulation of water or air through the open end of the condenser.
11
The leaching column comprises a cylindrical, stainless steel outer shell
protected by a 1/4-inch-thick graphite liner. The column has a charge capac-
ity of 20 pounds of crushed Al-Si alloy. A graphite-lined stainless steel
pipe joins the leaching column to the evaporation chamber and serves as a
return line (9) for the molten Zn-Al alloy.
This design was intended to permit separate controls for heating each
basic section of the unit (condenser, leach column, and evaporator) to within
a few degrees of the desired temperature.
Results of tests with the gas-fired extraction unit are shown in table 2.
The percentage of aluminum recovered increased approximately linearly within
the 448
0
to 475
0
C. temperature range. This is in agreement with results of
extraction for tests run in the induction-heated unit in which extraction rate
is uniform up to about 40 percent aluminum extraction.
STUDY OF PROCESS CONDITIONS
The preceding tests were devoted primarily to an investigation of the
effects of various combina-tions of leaching temperature and time of aluminum
extraction efficiency. Additional experiments were run to determine the
parameters for other process conditions including system pressure, particle
size, alloy composition, and the relative merits of liquid and vaporous zinc
as leaching agents.
TABLE 2. - Extraction experiments, gas-fired unitl
l
Leach Aluminum Average Composition of product,
Test No. temperature, recovered, extraction rate, percent
C. percent grams per minute Al Fe Si Ti
1 ...... 448 19.9 1.61 94.09 0.28 5.62 10.01
2 451 22 .5 1.81 94.92 .64 4.42 .02
3 ...... 458 25.3 2.03 95.46 .04 4.50 .005
4 ...... 462 27.4 2.20 93.78 .11 6.09 .02
5 .. 475 35.6 2.85 93.59 .15 6.2 .06
II Leaching period, 240 minutes; Zn-Al ratio, 2.12; charge for each test,
10 pounds.
Pressure
The beneficial effects of performing the extraction in a vacuum enclosure
are shown in table 3. In the a tests, part of an Al-Si alloy was held under a
12
cover of molten zinc for 2 hours at 500
0
and 600
0
C., at a pressure of 25
microns. The zinc was prevented from evaporating by a tightly-fitting cover.
The tests were then duplicated (tests b) in a system filled with an inert gas
at atmospheric pressure.
Results of these experiments show that dissolution of aluminum at low
pressure is approximately 20 times greater than at atmospheric pressure. How-
ever, the disso1utio n of silicon also increas es at reduced pressure. As
expected, the solubilities of silicon and aluminum are greater at higher
temperatures. It is believed that the increase in leaching rate at reduced
pressure can be attributed in part to the absence of gas films and absorbed
gases within the alloy, which would tend to prevent the zinc from wetting the
Al-Si surfaces.
TABLE 3. - Effect of pressure on dissolution of aluminum
Relative
Test Time, Tempera- Pressure, Aluminum Silicon extraction ratio AI-Si
No. minutes ture, millimeters extracted, extracted, Al Si ratio
OCt
Hg percent percent (a):(b) (a):(b)
a 120 500 0.025 7.86 0.25 20.2 1.25 31.4
b 120 500 760 .36 .20 1.95
a 120 600 .025 18.11 .89 23.2 4.5 20.3
b 120 600 760 .78 .20
3.9
Leaching
A series of tests was G0n-duGted to determin-e the relative effectiveness
of liquid zinc and zinc vapors as leaching agents. Table 4 shows the results
of tests using liquid zinc only. Leaching was accomplished by passing zinc,
at several selected rates, through a vertical evacuated column of crushed
Al-Si alloy. Leaching efficiencies were determined by analysis of the amount
of aluminum dissolved by the zinc during transit through the column. Tempera-
ture within the column was maintained at 475
0
C. for each test.
Results show that the ratio of aluminum extracted per gram of zinc
decreased as the flow rate of zinc increased. However, the total weight of
aluminum recovered was greatest at the highest zinc flow rate. Aluminum
extraction ranged from 1 percent at a rate of 25,.4 grams of zinc per minute
to 4 percent at a rate of 66.7 grams per minute.
The effect of zinc vapor on leaching was studied with a modified smal1-
scale reflux-leaching unit in which the vapors were condensed directly on the
A1-Si alloy during the leaching cycle instead of refluxing liquid zinc through
the alloy. This procedure exposed the alloy to high concentrations of zinc
vapor for a short period of time until liquid-vapor equilibrium conditions
were established in the leaching column. Distillation of zinc into the Al-Si
alloy bed was continued until approximately the same amount of zinc was dis-
tilled as had been passed through the alloy in the liquid-leaching tests.
However, due to the restricted evaporation surface area, it was impossible
to achieve distillation rates comparable to the liquid-zinc flow rates.
13
The results of these tests are shown in table 5. The aluminum extracted
ranged from 8 to 28 percent. Although the two groups of tests are not compa-
rable in every respect because of differences in leaching time and the amount
of zinc used, they reveal two significant observations. First, zinc in the
vapor state penetrates more thoroughly than liquid zinc into the smallest
interstices of the aluminum particles where it gradually condenses to the
liquid state. Second, the Al-Si particles are more thoroughly wetted by the
vapor than by the liquid zinc. These observations indicate that the zinc
vapor contributes markedly to the extraction efficiency by saturating the
AI-Si particles to a greater degree than liquid zinc. However, after the
initial penetration and saturation of the Al-Si alloy, liquid zinc probably
leaches as effectively as zinc vapor.
TABLE Lt. - Liquid-Zinc leaching ..
hI
Zinc Aluminum Aluminum extracted
Test No. Zinc flow rate, used, extracted, per gram zinc used,
grams per minute grams grams grams
l .... a ....... 25.4 721 4.69 0.0065
2-a. ,. ..... 38.0 1,114 6.57 .0059
3 ..... a .. 11 51.1 1,499 7.19 .0048
4-a ..... 66.7 2,164 9.31 .0043
11 Leach temperature, 475
0
C.; pressure, 0.05 millimeters.
TABLE 5. - Zinc-vapor leaching
11
Zinc Aluminum Aluminum extracted per
Test No. distilled, extracted, gram zinc distilled,
grams
21
grams grams
I-b" . 41. " II II " II III .. II " II II
768 33.7 0.044
2 .... b .. II II II II"."" II." II. II II 768 29.7 .039
3-b .................. 1,536 102.6 .067
4-b" . " II " " " ...... II II " II II
2,496 118.6 .044
11 Leach temperature, 475
0
C.; pressure, 0.05 millimeters.
~ I Based on experimentally determined distillation rate of 8.05
grams per minute.
During the regular aluminum extraction tests the extraction rates varied
among tests conducted at identical temperature, time, and pressure conditions.
An examination of the AI-Si charge material for these tests showed that vari-
ations of the average particle size of the charge resulted in differences in
the aluminum extracted from the alloy. Therefore, a series of tests was made
to compare the aluminum extracted from different-sized pieces of AI-Si alloy.
Each size group was tested for 3 hours at leaching temperatures of 450
0
, 475,
and 500
0
C. Results of these experiments are shown in table 6,
Within the optimum leaching-temperature range (450
0
-500 C.) the minus
3/4- plus 1/2-inch charge material yielded the highest aluminum recovery.
When small pieces of Al-Si alloy were used, much zinc was retained in the
leaching column, usually enough to form a shallow pool of liquid metal on top
of the crushed alloy. The solids were too compact to allow the free flow of
14
zinc through the leaching column back to the evaporator section. Tests with
minus 1- plus 3/4-inch material showed a better aluminum recovery than tests
with the smaller material, but recovery was less than in tests with minus 3/4-
plus 1/2-inch material treated in the same way. In the case of the large mate-
rial, penetration of zinc vapor and liquid into the alloy was not as rapid or
as complete owing to the smaller total surface area exposed and the larger size
of the Al-Si alloy particles.
The amount of aluminum extracted from the minus 3/4- plus 1/2-inch mate-
rial was 5 to 10 percent greater than that from the other sizes.
TABLE 6. - Effect of alloy particle size on leaching
1
/
Leach Average rate of
Test
Al-Si alloy particle ternpera- Aluminum Aluminum aluminum
No. average diameter,
ture, extraction, extraction, extraction,
inches C. grams percent grams per minute
1 -1/2, +1/4 450 63.1 15.0 0.35
2 -3/4, +1/2 450 105.9 25.2 .59
3 -
1, +3/4 450 65.2 15.5 .36
4 -1/2, +1/4 475 174.5 41.5 .97
5 -3/4, +1/2 475 217.6 51.7 1.21
6
-
1, +3/4 475 199.4 47.5 1.11
7 -1/2, +1/4 500 208.5 49.6 1.16
8 -3/4, +1/2 500 252.5 60.1 1.40
9 - 1, +3/4 500 209.0 49.8 1.17
1/ Leaching time, 3 hours; distillation temperature, 550
0
C.
Investigation of the effect of iron content on the efficiency of aluminum
extraction from Al-Si alloys showed an increase in leaching efficiency with an
increase in the iron content of the alloys. Table 7 gives results of tests in
which Al-Si alloys containing 5.25, 10.2, and 13.7 percent iron were leached
at 500
0
C. for 1 to 3 hours.
TABLE 7. - Effect of Al-Si alloy iron content on aluminum extraction
Iron in Al-Si alloy, Time, Aluminum extracted,
Test No. nominal percentl/ hours percent
1 ............... 5 1 6.45
2 ... 10 1 9.53
3 ........ 13 1 12.16
4 .... 5 2 10.24
5 ... 10 2 15.43
6 . 13 2 23.9
7 .. 5 3 40.3
8 .......... 10 3 46.1
9 .. 13 3 70.8
Charge analysis, percent:
Tests 1, 4, 7--Fe, 5.25; Si, 42.2; AI, 51.0; Ti, 1.5.
Tests 2, 5, 8--Fe, 10.2; Si, 33.9; AI, 50.6; Ti, 5.3.
Tests 3, 6, 9--Fe, 13.7; Si, 35.9; AI, 45.3; Ti, 5.1.
15
The only physical differences observed among the alloys were in porosity
and brittleness; these were greater in the alloy with the highest iron con-
tent. The greater porosity is believed to allow the zinc vapors to penetrate
more rapidly and thoroughly into the AI-Si particles to dissolve aluminum at a
faster rate. Specimens of the alloys prepared for X-ray diffraction analysis
showed no apparent phase differences between the alloys.
CONCLUSIONS
The following conclusions are drawn from the results of these
investigations:
1. The reflux leaching method is an effective means for extracting alumi-
num from crude AI-Si alloy. Aluminum obtained by this method will contain
from I to 6 percent silicon, 0.04 to 0.8 percent iron, and 0.01 to 0.9 percent
titanium. With only minor changes in composition by dilution of impurities
with pure aluminum, the leached aluminum would serve as a base alloy for pro-
ducing approximately 50 percent of the commercially used sand-casting alloys.
2. Dissolution of aluminum and silicon increases with increasing leaching
temperature, and the rate of dissolution is affected by alloy particle size,
iron content, and the system pressure.
3. The rate of aluminum extraction is approximately linear with respect
to time between 0- and 40-percent extraction. Complete removal of aluminum
can be obtained,although the advantage of complete extraction at low leaching
temperatures may be lost to the unwarrantable expense of time.
4. It is desirable to maintain the sys tem pressure at 100 microns or
lower. The rate of aluminum extraction is increased about 20 times by decreas-
ing the pressure from atmospheric pressure to a pressure of 100 microns or less.
5. Aluminum extraction can be accomplished with relatively little zinc as
the leaching agent by a continuous cycle of operation including evaporation,
condensation, leaching, and reevaporation.
6. The optimum AI-Si alloy particle size for leaching is one large enough
to permit a relatively free flow of zinc through the leaching column and small
enough to allow rapid penetration of the zinc into the leach material. Experi-
mental results indicate an optimum particle size of minus 3/4- plus 1/2-inch.
7. Aluminum extraction is increased by using Al-Si alloys containing
increased amounts of iron. The porosity of the alloy appears to become greater
as the iron content increases and allows more rapid penetration of zinc into
the alloy particles.
FUTURE RESEARCH
Continuation of the research and development program reported here
includes a number of larger scale extraction tests to supplement data obtained
in the small-scale work and to reveal difficulties which may be encountered in
large-scale operations. Equipment for these tests has been designed for 100-
pound charges of the alloy. Studies will be continued on the effect of various
AI-Si alloy constituents on leaching rates and efficiency of aluminum recovery.
An investigation of the properties of the silicon residues will be made to
determine the possibilities of developing processing methods to produce a
usable product from this material.
fNT.-BU.OF MINES,PGH. ,PA. 2456