U.S. patent number 3,616,277 [Application Number 04/748,034] was granted by the patent office on 1971-10-26 for method for the electrodeposition of copper powder.
This patent grant is currently assigned to Kennecott Copper Corporation. Invention is credited to David L. Adamson, William M. Tuddenham.
United States Patent |
3,616,277 |
Adamson , et al. |
October 26, 1971 |
METHOD FOR THE ELECTRODEPOSITION OF COPPER POWDER
Abstract
Metallic powder, e.g., copper powder, is deposited on a series
of disc-shaped cathodes as they turn through an electrolytic
solution of the metal. The cathodes, preferably of titanium, are
partially immersed in a bath of electrolyte contained in an
electrolytic cell tank. Insoluble anodes, preferably of platinized
titanium, are disposed in the tank in interleaved arrangement with
the cathodes. Powder is continuously deposited on the cathodes and
continuously removed by doctor blades, preferably of plastic,
mounted adjacent the cathodes above the electrolyte level of the
cell. In the production of copper powder, the cell operates at a
much higher temperature, current density, and acid
concentration--and with a much lower copper ion concentration in
the electrolyte--than is typical for the electrodeposition of
copper in electrolytic cells.
Inventors: |
Adamson; David L. (Salt Lake
City, UT), Tuddenham; William M. (Salt Lake City, UT) |
Assignee: |
Kennecott Copper Corporation
(New York, NY)
|
Family
ID: |
25007697 |
Appl.
No.: |
04/748,034 |
Filed: |
July 26, 1968 |
Current U.S.
Class: |
205/576; 204/234;
205/583; 204/216; 205/74 |
Current CPC
Class: |
C25C
5/02 (20130101) |
Current International
Class: |
C25C
5/02 (20060101); C25C 5/00 (20060101); C22d
005/00 (); B23p 001/00 (); B01k 003/00 () |
Field of
Search: |
;204/10,216,234 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Tufariello; T.
Claims
We claim:
1. A method for electrowinning copper values and recovering them in
powder form, comprising
introducing an electrolyte solution containing copper values into
an electrolytic cell, said cell having mounted therein at least one
rotating, disc-shaped titanium cathode and at least one insoluble
anode;
applying a current across the electrodes while maintaining a
current density above about 200 amperes per square foot of anode
area, and a sufficiently high electrolyte concentration to maintain
an electrical potential drop of about 4.8 volts across the
cell;
rotating the cathode in said electrolyte during the deposition of
copper powder thereon; and
recovering the copper powder from the cathode surface.
2. A method according to claim 1, wherein the electrolyte in the
cell tank is a sulfuric acid solution of copper containing between
about 1.2 and about 1.5 percent by weight copper.
3. A method according to claim 2, wherein the temperature of the
electrolyte is maintained between about 130.degree. and about
150.degree. F.
4. A method according to claim 3, wherein the electrolyte contains
between about 16 and 18 percent by weight sulfuric acid.
5. A method according to claim 1, wherein the electrolyte is
circulated from the electrolytic cell, through a leaching step
wherein additional metal values are dissolved, and back to the
electrolytic cell.
6. A method according to claim 5, wherein the electrolyte in the
cell tank is a sulfuric acid solution controlled to contain between
about 1.2 and about 1.5 percent by weight copper and between about
16 and about 18 percent by weight sulfuric acid and is held between
about 130.degree. to about 150.degree. F.
7. The method of claim 6, wherein the temperature of the
electrolyte in the cell tank is maintained at about 140.degree.
F.
8. The method of claim 6, wherein the rate of rotation of the
cathodes is controlled to provide a plating time of about 2 to
about 4 minutes.
Description
BACKGROUND OF THE INVENTION
Field
The present invention relates to the electrodeposition of metal
powders and provides an improved apparatus for that purpose. In
particular, it concerns the electrowinning of copper in the form of
high- purity copper powder and provides a specific method for
producing such a powder in the apparatus of this invention.
State of the Art
Various methods and apparatus for the electrodeposition of metallic
powders are known. Certain of the processes and apparatus involve
the deposition of metallic powder on a movable or continuous
cathode. U.S. Pat. No. 1,736,857, for example, discloses and claims
apparatus involving an endless cathode in the form of a band which
continuously passes between anodes through a trough containing
electrolyte. U.S. Pat. No. 2,810,682 discloses and claims a process
whereby silver powder is produced from a soluble silver anode. The
anode dissolves in the electrolyte and powder is formed on a
disc-shaped cathode rotating slowly through the electrolyte.
Deposited powder is removed as the rotating cathode surfaces pass
between a pair of metallic doctor blades. The powder settles to the
bottom of the electrolyte bath and is periodically recovered by
filtering the electrolyte. U.S. Pat. No. 1,959,376 discloses a
process and U.S. Pat No. 2,053,222 discloses an apparatus for
producing copper powder. According to these patents, a series of
disc-shaped copper cathodes is mounted in an electrolytic cell tank
such that each cathode is partially immersed in the electrolyte
bath contained therein. Soluble copper anodes are suspended in the
electrolyte bath on each side of each cathode. The cathodes are
rotated as a current is applied across the electrodes. Copper
deposited on the rotating cathode surfaces is removed as powder by
doctor blades mounted above the electrolyte surface.
The aforedescribed prior art processes each involves the
dissolution of relatively impure metal in the electrolyte contained
in an electrolytic cell tank and the continuous redeposition of
this metal as powder on a moving cathode. A difficulty common to
these processes is the entrapment of impurities present in the
electrolyte as the result of dissolving impure metal in the cell
tank. This difficulty is particularly significant because the
cathode deposits are necessarily of a nature which contains a
considerable volume of voids wherein the impurities may be
entrapped. Moreover, after soluble anodes dissolve to a
predetermined extent, typically 70 to 90 percent, they must be
replaced and scrapped. Otherwise, the anodes weaken and fail
structurally, resulting in electrical shorts and damage to cell
walls.
SUMMARY OF THE INVENTION
The present invention provides a process whereby high-purity copper
powder is produced by deposition on rotating cathodes. The process
involves the rigid control of operating variables; in particular,
temperature and composition of the electrolyte, current density,
and plating time. This invention further provides a novel
electrolytic cell, useful for the production of copper powder in
accordance with the claimed process, as well as for the production
of other metal powders by analogous processes.
The apparatus and process of this invention are particularly useful
for the production of copper powder from electrolytes formed by
leaching impure copper-bearing materials such as precipitate
copper.
According to this invention, copper powder is produced by flowing
an electrolyte through a tank in which are suspended insoluble
anodes and titanium cathodes alternating in parallel, interleaved
arrangement. The anodes are stationary and the cathodes are
movable, preferably as rotating discs. A higher-than-ordinary
current density is maintained across the electrodes; because of the
carefully controlled electrolyte temperature and composition taught
by this invention, current densities of about 200 to about 280
amperes per square foot at the anode and about 300 to about 400
amperes per square foot at the cathode are practical. To obtain
adequate circulation, it is essential that the anodes be insoluble
so that the anode reaction results in the evolution of oxygen gas.
The required vigorous circulation is induced by the evolution of
oxygen from the anode surfaces without additional agitation. The
preferred anode surface is of platinum, platinum-coated titanium
being presently considered the best material of construction.
Because the electrolyte becomes extremely corrosive as it dissolves
oxygen, the cathodes are constructed of titanium to avoid pitting
of the plating surfaces.
The temperature of the electrolyte is maintained above at least
about 130.degree. F., preferably at about 140.degree. F. At lower
temperatures there is insufficient mobility of the copper ions in
the electrolyte to maintain an appropriate concentration at the
cathode-solution interface. Temperatures above about 150.degree. F.
result in the generation of a serious acid mist above the cell and
are rarely employed, although it is recognized that higher
temperatures are advantageous provided control of the acid mist is
economically justified.
Proper control of the chemical composition of the electrolyte is an
important aspect of this invention. The copper ion level is
maintained low, i.e., about 1.2 to about 1.5 percent by weight,
based on the total weight of the electrolyte. The spent electrolyte
leaving the cell is recycled through a leaching step and back to
the cell tank. The sulfuric acid level is maintained at about 16 to
about 18 percent by weight on the aforestated basis, thereby
facilitating regeneration of the electrolyte by leaching. The high
acid content also results in low cell resistance, thereby
permitting effective deposition of copper at a lower voltage. The
acid content of the electrolyte should be sufficiently high to
result in a voltage drop of less than about 5 volts across the
cell.
The deposition of copper powder in accordance with this invention
is accomplished by maintaining the process conditions hereinbefore
described in an electrolytic cell of special construction,
including a continuously moving titanium cathode surface and
insoluble anodes. Although the electrolytic cell of this invention
is particularly useful for producing copper powder it may be
employed for the production of other metal powders by following
procedures similar to those specifically described in connection
with the production of copper powder.
In the deposition of copper powder, it has been found that growth
time is an important factor influencing the particle size
distribution of the copper powder recovered. Longer plating times
result in wider distributions including higher percentages of
coarse fractions. Although the plating time may be selected to
produce the product desired in a particular instance, the product
most desired for powder metallurgy applications, i.e.,
substantially all -100 mesh and including about 40 to about 70
percent by weight -325 mesh, is produced with plating times of
about 2 to about 4 minutes.
The apparatus of the present invention includes a tank constructed
to maintain a predetermined, desired electrolyte depth therein; a
plurality of insoluble anodes, preferably of platinized titanium,
mounted vertically in the tank to immerse the surface area of the
anodes in the electrolyte contained in the tank; a plurality of
disc-shaped titanium cathodes suspended in the tank in alternating,
parallel interleaved arrangement with the insoluble anodes and
mounted to rotate about their axes such that as they are rotated in
operation, progressive wedge-shaped segments of the plating surface
areas of the cathodes traverse a circular path whereby they
cyclically dip beneath the electrolyte surface level of the tank,
traverse the tank past an adjacent anode, and then traverse a
circular arc above the electrolyte surface level of the tank to
again dip beneath the electrolyte surface level of the tank; the
necessary bus bars and other electrical equipment required to
provide a current between the anodes and cathodes; and scraping
means, e.g. doctor blades, mounted adjacent the cathodes and above
the electrolyte surface in position to scrape the plating surfaces
of the cathodes as they rotate about their axes. Desirably the
scraping means are associated with means for collecting any
deposits removed from the cathodes by the scraping means.
DESCRIPTION OF THE DRAWINGS
In the drawings, which illustrate the best mode presently
contemplated for practicing the invention:
FIG. 1 is a side elevation of the novel electrolytic cell of this
invention;
FIG. 2, a sectional view taken along the line 2--2 of FIG. 1;
and
FIG. 3, a sectional view taken along the line 3--3 of FIG. 2.
DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS
The illustrated apparatus comprises an electrolytic tank 11 in
which are disposed a plurality of anodes 12 and a plurality of
cathodes 13 in alternating, parallel, interleaved arrangement. The
cathodes 13 are titanium discs mounted on a round copper shaft 14
(FIG. 2). The entire series of cathodes is mounted on a reduced
section 14a of the shaft, the individual cathodes being separated
by cylindrical titanium spacers 15 which fit over the shaft between
adjacent cathode discs. A similar spacer 16 extends from the
cathode disc 13-1 at one end of the series of cathodes to a copper
washer 17 which fits snugly against a bearing block 18. One end
section 14b of the shaft, which is larger in diameter than the
remainder of the shaft, is journaled in bearing block 18, being
held in position by washer 17. The bearing block 18 is of copper
and serves as a commutator for electrical connection to the power
supply (not shown). The journaled connection is lubricated with
graphite. Another spacer 19 extends from the cathode disc 13--2 at
the other end of the series of cathodes toward a plastic bearing
block 20 in which the opposite end section 14c of the shaft is
journaled. The spacers and cathodes are fastened into position by a
titanium washer 21 and a threaded titanium nut 22. The end section
14c of the shaft is appropriately reduced in diameter to
accommodate the nut 22.
At the end of the copper shaft 14 opposite the commutator is a hub
23 and sprocket 24 arrangement for driving the shaft. A plastic
spacer 25 fits between the bearing block 20 and the hub 23 to
prevent the shaft from sliding. The hub is electrically insulated
from the sprocket by plastic insulators 26. The sprocket is driven
(FIG. 1) by a variable-speed reduction motor 27 and chain 28. The
entire apparatus is mounted in a structural frame 29 which is
insulated from the shaft by the plastic bearing block 20 and a
plastic support block 30 between the bearing block 18 and the
structural frame 29.
The cathodes are vertically suspended from the shaft so that they
are immersed in the electrolyte to a depth of about one third of
their diameters. The anodes are constructed of insoluble sheet
metal, preferably platinized titanium and are suspended in the tank
by plastic rods 31 and 32 (FIG. 3). The rods are held in place by
plastic brackets 33 anchored to the tank wall 11a as illustrated by
FIG. 2. The anodes are spaced along the support rods by cylindrical
plastic spacers 34. Spacing of the bottoms of the anodes is
maintained by plastic rods 35 and 36 (FIG. 3) and cylindrical
plastic spacers 37 as illustrated by FIG. 2. Each anode 12 is
welded at one end to a titanium rod 38 to which electrical
connection is made by means of a copper lug 39 and cable 40. Power
is supplied to the electrodes in conventional fashion by a
rectifier (not shown).
In operation, copper-bearing solution is metered from a head tank
(not shown) to the cell tank through a manifold port 41 (FIG. 1).
Spent electrolyte overflows through a port 42 (FIG. 3) into a surge
chamber 43 to maintain a preselected electrolyte level in the cell
tank 11. The spent electrolyte is continuously withdrawn from the
surge chamber 43 through a pipe 44 for recycle through a leaching
step (not shown) and back to the cell tank 11. In this fashion, the
desired metal ion, e.g., copper ion, concentration is maintained in
the electrolyte solution in the cell tank.
As the electrolyte solution is circulated through the tank,
cathodes 13 are rotated by shaft 14 thereby submerging progressive
segments of the plating surfaces 13a of the cathodes in the
electrolyte contained in the tank. Simultaneously, a current is
applied between the anodes and cathodes to effect the deposition of
metal powder 45 on the submerged portions of the plating surfaces
of the cathodes. As the cathode discs continue to rotate, the metal
deposited on a particular segment of the cathode surface is lifted
up from the electrolyte and moved through an arc above the
electrolyte. Plastic doctor blades 46 are mounted above the
electrolyte surface and adjacent the cathodes to continuously
scrape the metal deposit from progressive segments of the cathode
surfaces as the cathodes rotate. As illustrated, the doctor blades
contact the plating surfaces of the cathodes just above the
electrolyte surface on the side of the cell at which the cathodes
enter the electrolyte. After the metal deposit 45 is removed from
the plating surfaces of the cathodes by the doctor blades, the
scraped segments 13a' are again submerged beneath the surface of
the electrolyte to receive additional metal deposit. The metal
accumulating on the doctor blades 46 is removed by water jets 47
from nozzles 48 in a manifold tube 49 mounted to direct a water
spray against both the cathode surfaces and the scraper blades. The
manifold tube 49 is structurally supported by a pipe (not shown)
which supplies it with water. The metal powder is discharged by the
doctor blades 46 into a surge chamber 50 and is flushed out of the
surge chamber through an outlet 51 for collection.
As an example of the apparatus and method claimed by the present
invention, an electrolytic cell of the general configuration
illustrated by the drawing is constructed and operated as follows:
Two 36-inch diameter titanium discs, 0.180 inch thick, are mounted
on a section of a round, copper shaft, having a diameter of 11/4
inches. The cathode discs are spaced as illustrated by hollow
titanium cylinders with outside diameter of 2 inches to hold them
in interleaved relation with three platinized titanium anodes. The
anodes are constructed of 0.125-inch titanium sheet having a 50
microinch layer of platinum on both sides and have surface areas
(including both sides) of about 5 square feet. The anodes are
connected to the power source through copper lugs. Power is
supplied by a selenium rectifier having a 2,000 ampere capacity.
The cell tank is of stainless steel and holds about 35 gallons of
electrolyte at a depth such that the anodes are completely
submerged whereas the cathodes are immersed about 12 inches,
measured upwardly from the circumference along the vertical
radius.
Current is applied sufficient to provide a current density of about
250 amperes per square foot at the anodes and about 330 amperes per
square foot at the cathodes. The electrolyte is a sulfuric acid
leach solution of copper and its temperature in the tank is
maintained at about 140.degree. F. The flow rate of electrolyte
through the cell is controlled to maintain a copper ion level of
between about 1.2 and 1.5 percent by weight, varying between about
0.2 and about 0.25 gallons per minute. The sulfuric acid level in
the electrolyte is maintained at between about 16 and about 18
percent by weight so that the electrical potential drop across the
cell is maintained below about 4.8 volts. The speed of rotation of
the cathodes is adjusted to submerge each point on the
circumference of each cathode for a period of between about 2 to
about 4 minutes, during each rotation, i.e., to provide a plating
time of about 2 to about 4 minutes. Spent electrolyte is circulated
through a tank wherein it is regenerated by the addition of
appropriate quantities of acid and by contact with copper
precipitate, i.e., finely divided impure copper powder recovered
from copper-bearing mine water by precipitation on iron. The
regenerated electrolyte is recycled to the electrolytic cell
tank.
Although the present invention has been described with reference to
details of certain specific embodiments it is not intended thereby
to limit the scope of the claims except insofar as the details are
recited therein. Many modifications within the legitimate scope of
the invention will be suggested to those skilled in the art by the
present disclosure.
* * * * *