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(19) J European Patent Office


Office europeen des brevets (11) EP 0 775 763 A1

(12) E U R O P E A N PATENT A P P L I C A T I O N

(43) Date of publication:


ation: (51) Int. CI.6: C25C 7/00, C25C 1/20
28.05.1997 Bulletin 1997/22

(21) Application number: 96116523.0

(22) Date of filing: 15.10.1996

(84) Designated Contracting States: • Cromwell, John L.


AT BE DE ES Fl FR GB SE Pincourt, Quebec J7V 5Z7 (CA)

(30) Priority: 27.11.1995 US 563079 (74) Representative: Grape, Knut, Dipl.-lng. et al


Lewald - Grape - Schwarzensteiner
(71) Applicant: NORANDA INC. Patentanwalte
Toronto Ontario, M5J 2T3 (CA) Rindermarkt 6
80331 Munchen (DE)
(72) Inventors:
• Claessens, Pierre
St-Eustache, Quebec J7P 2L9 (CA)

(54) Silver electrolysis method in moebius cells

(57) The present invention is concerned with a


method for electrorefining silver in a Moebius cell
whereby the anode is completely dissolved and the gold 26 30
mud is removed without handling of any partially dis-
solved anodes. The cell is conventional except that the
anodes are placed in a basket (10) made of a thermo-
plastic material and surrounded by a cloth, the electrical
contact between the anode and the power source takes
place outside the electrolyte. The bottom of the basket
is provided with apertures allowing the gold mud pro-
duced to fall into the cloth until the anode is completely
dissolved.

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1 EP 0 775 763 A1 2

Description loaded in the refining cell, and therefore it must be


remelted, recast and reelectrolysed, thus increasing the
FIELD OF THE INVENTION overall costs for obtaining pure silver. On the other
hand, in Balbach-Thum cells, the cathode is at the bot-
The present invention is concerned with a novel 5 torn of the cell, and the anodes are deposited at the bot-
method for the refinement of silver in conventional Moe- tom of a basket, parallel to the cathode, the bottom of
bius cells. the basket being lined with a cloth to collect the gold
mud. Although complete dissolution of the silver anodes
BACKGROUND OF THE INVENTION appears to occur in Balbach-Thum cells, there are sig-
10 nificant manipulations of partially corroded silver
One of the major elements present in the slime anodes for the following reason. As stated above, the
resulting from copper electrorefining is silver. To recover anodes are deposited onto the cloth in the basket. Since
that silver, the slime is treated by various methods to the anode contains important amounts of impurities,
give impure silver anodes. Such anodes are referred to these impurities remain in the basket as anodes dis-
in the art as "Dore" anodes. The composition of a Dore 15 solve to leave a residue that is referred to in the art as
anode greatly varies depending on the source of the gold mud. After a certain time, the dissolution of silver is
slime and of the purity of the original copper anodes, but impaired by the increasing amount of gold mud in the
the silver content is generally from about 80% up to cloth, and accordingly, gold mud, together with the cor-
99%. Dore anodes may also be obtained from lead roded modes present therein, must be removed from
refining or the treatment of precious metal bearing 20 the basket and the undissolved portion of the modes
scrap. Other components or elements of these anodes must be washed before being returned in the cell.
include copper and precious metals like gold, palladium Both types of cells have in common that the han-
and platinum. dling of partially corroded modes and the recovery of
Dore anodes are refined by electrolysis to produce gold mud are time-consuming operations, and there-
pure silver metal at the cathode, but this refining also 25 fore, any improvement in that respect will result in lower
produces anode mud containing gold and other pre- costs for silver refiners.
cious metals present in the Dore anode. The silver elec- US 5,100,528 (Claessens et al.) discloses a contin-
trorefining operation is conventionally carried out by uous silver refining cell wherein silver modes are depos-
using either a Moebius cell, which is described by Man- ited in a titanium mode basket that is subsequently
tell in Electrochemical Engineering, 4th edition, McGraw 30 immersed in a tank containing the electrolyte. Another
Hill Book Company, New York 1960, pp. 166-173; or a silver electrorefining cell has been developed to reduce
Balbach-Thum cell, which is described by de Kay as much as possible anode scrap, as described by Ima-
Thompson in Theoretical and Applied Electrochemistry, zawa et al in "Continuous Silver Electrorefining Opera-
3rd edition, The Macmillan Company, New York, 1939, tion", Metallurgical Review of the MMIJ, 1984, Vol. 1,
pp. 257-260. Several considerations will influence the 35 No. 1, pp. 150-159. In this cell, the basket is also made
choice of either cell. The Moebius type cell is generally of conductive titanium material to insure contact of the
preferred because it requires significantly less floor impure silver mode with the positive terminal of the con-
space, about 1/5 of that of a Balbach-Thum cell, and tinuous current electrical power source. This cell, as
less energy for a given amount of silver refined. well as the cell described in US 5,100,528, is very com-
Although the Moebius cell requires more time for remov- 40 plex as it allows for the simultaneous continuous with-
ing silver and slime, it needs very little attention during drawal of the silver crystals deposited at the cathodes. A
normal operation, as silver crystals building up on the further drawback is that they are expensive to build and
cathodes are scraped mechanically and fall to the bot- may be difficult to operate.
tom of the cell. The Balbach-Thum cell requires fre- The use of conductive baskets is also well known in
quent manual removal of silver deposited onto the 45 the plating industry, where replenishment of ions of a
bottom of the cell, which acts as the cathode. metal to be plated is assured by using soluble modes
Other significant differences exist between Bal- made of the same metal. In this case, solid modes may
bach-Thum cells and Moebius cells, both in the struc- be suspended from the top of the cell, or smaller pieces
ture and in the physical requirements of the cells, as of the same anode material can be loaded in a partially
described in pages 86-87 of Silver: Economics, Metal- so submerged basket made of inert conductive material.
lurgy & Use, (A. Butts & C. D. Coxe), Van Nostrand Titanium is conventionally used as material of construc-
Company Inc. In a Moebius cell, the anodes and cath- tion for these baskets. A disadvantage of the use of
odes are suspended in an alternate manner in the cell. such conductive baskets in Moebius cells is that some
The anodes are only partially submerged in the electro- energy is lost at the surface of the basket by the degra-
lyte which results in a substantial portion of the impure 55 dation reaction of H20. In addition to the undesirable
anode being left undissolved ("scrap") at the end of an consumption of energy, this reaction produces 02 and
electrorefining cycle, typically lasting from 24 to 48 H+ ions, the latter increasing the acidity of the electro-
hours. The weight of the remaining anode scrap can lyte and impairing the efficiency of the process, since
amount to as high as 30% of the Dore anode originally metals like palladium and platinum will dissolve in an

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electrolyte having a lower pH, thus significantly contam- forced with fibers such as fiberglass. The cloth sur-
inating the silver. rounding the basket may be made of material similar to
US 4,692,222 describes the use of a basket made that of the basket, or any other inert material capable of
of electrically conductive material substantially inactive sustaining the corrosive environment of silver electro-
to the electrical process, to contain pieces of copper s lyte. To ensure that no acid is generated in the electro-
used as replenishment of copper ions in a plating cell. lyte, the electrical contact between the power source
As an alternative, the electrically conductive material and the electrode takes place above the surface of the
may be replaced with plastic, provided that the plastic electrolyte.
baskets contain some means of making electrical con-
tact to the pieces of copper therein, such as by way of a 10 IN THE DRAWINGS
conductive rod extending down into the basket. In this
instance, because of the presence of the electrical con- Figure 1 illustrates a perspective view of a basket
tact in the electrolyte through the conductive rod, the suitable for the present method; and
degradation reaction of water will take place, and the Figure 2 illustrates a perspective view of a plurality
acidity of the electrolyte will increase. is of baskets of Figure 1 joined.
US 4,207,153 is concerned with an electrorefining
cell that consists of bipolar electrodes having the mode DETAILED DESCRIPTION OF THE INVENTION
side made of a basket constructed with an acid resistant
metal in which fine cemented copper is added in a slurry In the method of the present invention, the conven-
form. Again in this case, the material of construction of 20 tional Moebius cell has been modified to replace hang-
the mode baskets is a metal, such as stainless steel or ing anodes with a basket having its upper edges
titanium. extending above the electrolyte level in the tank, and
In view of the above, there is therefore a great need wherein the anodes are deposited in a continuous man-
to improve the electrorefining of silver, particularly in ner. The basket comprises openings on each sidewall to
Moebius cells. For example, it would be desirable to 25 allow the passage of electrolyte and is surrounded by a
develop a method combining the advantages of both cloth or bag to collect the gold mud produced from the
Moebius and Balbach-Thum cells, namely allowing the silver electrolysis. The electrical contact between the
complete dissolution of silver modes that would be fed mode and the power source is made above the electro-
in a continuous manner in the electrolyte while eliminat- lyte level through a portion of undissolved mode or
ing any silver anode residue from the gold mud pro- 30 through another anode placed above the first mode.
duced therefrom, thus preventing the manipulation of The electrical contact between the cathode and the
partially corroded modes. With such a method, there power source is also made above the electrolyte level.
would no longer be a need to recycle mode scrap by Many advantages results from carrying out the present
melting and casting, resulting in significant savings in method in Moebius cells equipped with such baskets.
silver production. Further, as mentioned above, the floor 35 Anodes can be fed in a continuous manner; the produc-
space required for a Moebius cell is significantly smaller tion of mode scrap is eliminated, and the gold mud is
than that of a Balbach-Thum cell. recovered in the cloth around the basket without the
need to remove any partially corroded mode remaining
SUMMARY OF THE INVENTION in the basket. The use of a nonconductive material for
40 the basket prevents the generation of oxygen and the
In accordance with the present invention, there is production of acid caused by the degradation reaction
now provided a method for the continuous electrorefin- of H20 in the electrolyte. Experience has shown that
ing of silver in a Moebius cell by allowing a complete dis- electrorefining of silver in titanium basket causes the
solution of the silver mode without generating acid in the acidity to increase by as much as 1 to 2 g/L. An increase
electrolyte. More specifically, the method comprises 45 in acidity of the electrolyte near the anodes is detrimen-
inserting a silver mode in a basket made of nonconduc- tal as it promotes an increase in the level of palladium
tive material and surrounded by a cloth retaining the dissolution into the electrolyte, which results in an
gold mud produced during electrolysis. With such a increase in the contamination of the pure silver metal
design, the cloth is not in contact with the mode, and produced at the cathode.
therefore, the gold mud may be removed from the cell so 50 Sometimes, an increase in the acidity of the electro-
without the necessity of removing or handling the par- lyte can be caused by special circumstances resulting in
tially corroded modes remaining in the basket passivation of the modes, with simultaneous production
In a preferred embodiment, the basket is made of a of oxygen by decomposition of water at the anode/elec-
thermoplastic material resistant to the highly corrosive trolyte interface. However, passivation was definitely not
environment of a silver electrorefining cell. Thermoplas- ss the cause of the acidity increase in the tests carried out
tic materials include high and low density polyethylene, by the present inventors with a titanium basket. From a
polypropylene, polycarbonate, polyurethane, polyester, closer examination of the phenomenon, it can be con-
TEFLON, polyvinyl chloride (PVC), chlorinated PVC cluded that the increase in acidity observed with the tita-
and the like. Any of these materials may also be rein- nium basket is probably caused by a parasitic water

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decomposition reaction at the surface of the titanium anode, thus contaminating the electrolyte solution. Cop-
metal, instead of normal silver dissolution of the mode. per lath or strip 32 is then electrically connected to the
The fact that some part of the current applied to the bas- positive end of a power source via conductive material
ket is diverted to the surface of the basket, instead of to 36, and a cathode, electrically connected to the nega-
the silver mode, may be explained by the presence of a 5 tive end of the power source, is inserted in the bath (not
poorly conductive slime layer building-up at the surface shown). The cathode may be any cathode convention-
of the anode, thereby decreasing the quality of the elec- ally used in the field of silver refining, or in Moebius
trical contact between the titanium basket and the silver cells. As current is applied, the submerged anode inside
mode. the basket progressively dissolves and slides down-
Referring to Figure 1, which illustrates a preferred 10 wardly. To maintain electrical contact, a new anode is
embodiment of the invention, basket 10 made of poly- inserted on top of the one in the basket as the latter pro-
carbonate plastic, for example LEXAN manufactured gressively falls below the electrolyte surface. The sur-
and sold by General Electric, comprises compartments faces of the cathodes are scraped from time to time in
12 and 13 adapted to receive an anode therein. Com- the conventional manner. Operation of such experimen-
partment 12 is made of a pair of walls 16 and 17 pro- 15 tal baskets in a commercial Moebius cell over extended
vided with a plurality of slots 18 and/or round openings periods of time has shown to be totally problem free. No
20, or combinations thereof, and sidewalls 22. It is pref- anode scrap is produced, nor is the acidity of the elec-
erable to avoid orienting slots 18 in a vertical position, trolyte increased inside the cell. Further, the anode is
as the solid vertical divisions could act as shields never in contact with the gold mud, thus insuring that
against the current, causing vertical sections of the 20 substantially all the silver present in the anode is dis-
modes to dissolve at a reduced rate. Horizontal slots are solved and deposited at the cathode, thus completely
also preferably avoided as they may mechanically pre- eliminating any undesirable manipulation of partially
vent anodes from sliding down the basket as they pro- corroded silver anode while the method is in operation.
gressively dissolve. In a preferred embodiment, the The method is stopped from time to time to collect the
section of compartment 12 is tapered, that is, sidewalls 25 refined silver at the bottom of the cell. The continuity of
22 are wider at the top of compartment 12. The purpose the process is therefore easily maintained by simply
of this taper is to possibly prevent two dissolving anodes feeding the top of compartment 13 with silver anodes
to slide one over the other. The bottom of compartment when necessary to preserve the electrical contact. As
12 is open, but at least one spacer 24 is provided illustrated in Figure 2, a plurality of baskets 10 may be
between walls 16 and 17 to support the anode. The 30 joined.
large open surface area of the bottom of compartment The electrical contact is thus made with the top of
12 serves to eliminate any gold mud freed from the sur- the anode and the passage of current to the bottom of
face of the dissolving anodes. the anode, which is submerged, is assured without the
Compartment 13 is sitting on, moulded with, or presence of any foreign conductive material. This
secured to the top of compartment 12, and comprises a 35 arrangement significantly differs from that described in
pair of walls 26 and 27 separated by a pair of sidewalls US 4,692,222 mentioned above, in that the contact is
28 having a width corresponding to that at the top of made from a nonsubmerged or partly submerged
sidewalls 22. Walls 26 and 27 also comprise a slot 30 anode to the active submerged anode and no conduc-
adapted to receive at least one copper lath or strip 32 tive material other than the impure silver anode extends
having one end 34 secured to a piece of a conductive 40 down into the basket in the electrolyte solution.
material 36, preferably copper, which is itself secured The experimental conditions for carrying the
on the external side of walls 26 and 27, the material 36 method of the present invention are those used conven-
being electrically connected to the power source (not tionally in any Moebius cells. For example, in the case of
shown). The other end 38 of copper lath or strip 32 is silver, the conditions are as follows:
inside compartment 13 and in contact with an anode 45
inside compartment 13 (not shown) above the electro- temperature of the electrolyte: 30-50 °C
lyte surface. Finally, a cloth (not shown) is installed voltage: 3-5 volts
around the basket to retain any gold mud produced dur- current density: 300 - 900 Amps/m2
ing electrolysis of the anodes. cathode material: titanium, stainless steel or silver
In operation, a first anode is slid into compartment so acidity level: 0.1 to 10 g/L of nitric acid
12 through compartment 13, and a second anode is - electrolyte: 50-1 50 g/L Ag+ & 10-50 g/L Cu++ (both
placed on top of the first anode. Compartment 12 is as nitrates)
then surrounded with a cloth and placed in an electroly-
sis bath (not shown) by slowly immersing compartment These above parameters are provided to illustrate
12 in the electrolyte solution. Slots 18 and/or openings 55 the preferred experimental conditions, and should not
20 will allow for the free passage of ions upon applica- be construed as limiting the scope of the invention.
tion of current in the electrolyte. At no time is the elec- The appropriate shape and dimensions of a basket
trolyte solution in contact with copper lath or strip 32, are to be adjusted to the size and shape of the anodes
since the latter would dissolve preferentially to the silver to be refined. Any one of ordinary skill in the art can

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make those adjustments. Similarly, the method of tive means is at least one copper strip.
assembly of the various parts of the basket may vary
from that used in the experimental basket, wherein the 3. A method according to claim 2 wherein the conduc-
parts have been fastened with screws, the latter being tive means is a pair of copper strips each secured
isolated from the electrolyte. Gluing of the various parts 5 on a piece copper that is itself secured on opposite
or moulding of the basket as one piece can also be side walls of the basket, the piece of copper being
envisaged. Finally, the material of construction of the in electrical contact with the power source.
basket, its geometry, and the method of construction
and assembly can differ from the example shown, as 4. A method according to claim 1 wherein the noncon-
long as the basket is constructed of nonconductive w ductive material is a thermoplastic material.
material presenting an appropriate resistance to the
chemical environment prevailing in the silver electrore- 5. A method according to claim 4 wherein the thermo-
fining cell. Further, it is imperative that the electrical plastic material is selected from the group consist-
contact between the anode and the power source be ing of high and low density polyethylene,
made outside the electrolytic bath and that the cloth sur- 15 polypropylene, polycarbonate, polyurethan, polyes-
rounding the basket is not in contact with the anode. ter, TEFLON, polyvinyl chloride and chlorinated
While the invention has been described in connec- polyvinyl chloride.
tion with specific embodiments thereof, it will be under-
stood that it is capable of further modifications and this 6. A method according to claim 1 wherein the cloth is
application is intended to cover any variations, uses or 20 a thermoplastic material.
adaptations of the invention following, in general, the
principles of the invention and including such depar- 7. A method according to claim 6 wherein the thermo-
tures from the present disclosure as come within known plastic material is selected from the group consist-
or customary practice within the art to which the inven- ing of high and low density polyethylene,
tion pertains, and as may be applied to the essential 25 polypropylene, polyurethan, polyester, TEFLON
features hereinbefore set forth, and as follows in the and the like.
scope of the appended claims.
8. A method according to claim 1 wherein the cathode
Claims is scraped periodically to remove the silver depos-
30 ited thereon.
1. A method for the continuous electrorefining of silver
in a conventional Moebius cell comprising the steps 9. A method for the continuous electrorefining of silver
of: in a conventional Moebius cell comprising the steps
of:
depositing an anode of silver in a basket made 35
of nonconductive material and comprising a depositing a silver anode in a basket made of
plurality of apertures in side walls and bottom nonconductive material and comprising a plu-
thereof, the basket being provided with conduc- rality of apertures in side walls and bottom
tive means secured thereon and connected to thereof, the basket being provided with copper
a power source at one end and in electrical 40 strips secured on two opposite side walls and
contact with the anode at the other end; connected to a power source at one end and in
surrounding the basket with a cloth to retain the electrical contact with the anode at the other
gold mud remaining from the electrolysis of the end, the copper strips being adapted to allow
anodes and allowing dissolved silver to flow the anode to be continuously slid therebetween
freely therethrough; 45 in the basket;
immersing the basket in electrolyte and apply- surrounding the basket with a cloth to retain the
ing current to dissolve the anodes and induce gold mud remaining from the electrolysis of the
silver deposition at the surface of the cathode, anodes and allowing dissolved silver to flow
with the proviso that the conductive means are freely therethrough;
in electrical contact with the anode above the so
50 immersing the basket in electrolyte and apply-
surface of the electrolyte and the conductive ing current to dissolve the silver anode and
means are not in contact with the electrolyte; induce silver deposition at the surface of the
continuously inserting anodes in the basket cathode, with the proviso that the electrical
while it is still immersed whereby the electrical contact between the copper strips and the
contact between a dissolving anode, a newly 55 anode is above the surface of the electrolyte
inserted anode and the conductive means is and the copper strips are not in contact with the
maintained. electrolyte; and
continuously inserting silver anodes in the bas-
2. A method according to claim 1 wherein the conduc- ket while it is still immersed whereby the electri-

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EP 0 775 763 A1 10

cal contact between a dissolving anode, a


newly inserted anode and the copper strips is
maintained.

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J ) European Patent EUROPEAN SEARCH REPORT A,""1Ca,i0,, ^


Office EP 96 11 6523

DOCUMENTS CONSIDERED TO BE RELEVANT


Category Citation of document with indication, where appropriate, Relevant (XASSIMCAHUN Ut IHfc
of relevant passages to claim APPLICATION (Int.CL6)
JS 3 708 415 A (W.A. HUBBARD) C25C7/00
* column 4, line 23 - line 38 * C25C1/20
* figures 5-8 *

SB 2 206 356 A (ENGITEC IMPIANTI S.P.A.)


* page 11 - page 12; claims 1-8 *
* figure 2 *

D,A EP 0 391 028 A (NORANDA INC)


* column 4 - column 5; claims 1-6 *

TECHNICAL HfcLDS
SEARCHED (Int.CI.6)
C25C

The present search report has been drawn up for all claims
Place ofsearch Dateof conpletfoa ofthe search
THE HAGUE 29 January 1997 Groseiller, P
CATEGORY OF CITED DOCUMENTS T : theory or principle underlying the invention
E : earlier patent document, but published on, or
X: particularly relevant if taken alone after the filing date
Y: particularly relevant if combined with another D : document cited in the application
document of the same category L : document cited for other reasons
A: technological background
O : non-written disclosure &: member of the same patent family, corresponding
P : intermediate document document

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