CA1064860A - Electrolytic cell for use in hydroelectrometallurgy - Google Patents
Electrolytic cell for use in hydroelectrometallurgyInfo
- Publication number
- CA1064860A CA1064860A CA262,290A CA262290A CA1064860A CA 1064860 A CA1064860 A CA 1064860A CA 262290 A CA262290 A CA 262290A CA 1064860 A CA1064860 A CA 1064860A
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- CA
- Canada
- Prior art keywords
- cathode
- zone
- metal
- anode
- seed particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/002—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least an electrode made of particles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Abstract of the Disclosure An improved electrolytic cell for use in the continuous hydroelectro-metallurgical production of a metal by the electrolytic deposition of the metal on the surface of suspended seed particles of pure metal comprising a vertical cylindrical cell comprising an upper anode zone including a horizontal anode and a lower cathode zone including a horizontal network cathode, said network cathode partitioning the cathode zone into an upper and a lower part, and a stirrer positioned below said network cathode. Thus, the seed particles are.
part of the cathode zone, where they are electronegatively charged by their collision with the network cathode, with the consequence that the electrolysis is carried out with extreme effectiveness.
part of the cathode zone, where they are electronegatively charged by their collision with the network cathode, with the consequence that the electrolysis is carried out with extreme effectiveness.
Description
1t~6486~
This invention relates to an improved electrolytic cell for use in the continuous hydroelectrometallurgical production of a metal by the eleckrolytic deposition of the metal on the surface of suspended seed particles of the pure me~al.
Such a hydroelectrometallurgical method and appara-tus for use in such a method has been disclosed by me in United States Patent 3~787,293.
Hydroelectrometallurgy, as is well known, includes ~ ;
electrorsfining and electrowinning. While the former is a method which comprises carrying out an aqueous electrolysis by using a crude metal containing impurities as an anode thereby depositing a pure metal on a cathode, the latter is a method which comprises carrying out the electrolysis by employing as the electrolyte a solution in which a metal has been dissolved in advance in the foDm of its ion thereby depositing the metal on a cathode and thereafter recovering same.
A new method for carrying out the hydroelectrome-tallurgy has been fully described in the aforesaid United States Patent 3,787,293~
Such a method, in brief, comprises suspending particles of a starting crude metal or metal sulfide in the anode zone and seed particles of the pure metal in ~he cathode zone, causing said particules to collide with the surfaces of the anode and cathode, respectively, passing an electric current through said anode and cathode, the g~ .
. . . .
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particles of -th~ cr-ude ~letal or ~letal sulfide ~eing electro-~ositively charged due to their collision with the anode and becoming dissolved in an electrolyte solution, the seed particles bein~ electronegatively charged due to -their collision wi-th the cathode, whereby the metal ions in the electrol-~te solution are cathodically deposited as the metal on said seed particles, and thereafter recovering from the cathode zone the enlarged metal particles which have grown as a result of said electrolytic deposi-tion of the metal on the seed particles In the conventional hy~roelectrometallur~ical ; methods an anode plate and a ca-thode plate were suspended perpendicularly in an electrolyte solution and by passing an electric current between the two electrodes the metal was deposited on the cathode plate, after which the cathode plate was pulled up from the electrolytic cell and the . ;-deposited metal was recoveredO In this case the current .-~
per square decimeter was restricted to about 2 - 5 amperes, and the operation was carried out in a batchwise mannerO :~
As compared with such conventional methods, the above~men- `
tioned new method possesses an exceedingly distinctive feature in that the pure me-tal is deposited on -the seed ;~
metal particles -that are kep-t in suspension in the cathode :
zone9 after which the grown metal particles are recovered.
Since the whole area of the suspended particles is ~ar - - ~
greater than that of an electrode plate, the electric cur- ~.
rent that can be applied is very great, say, more than 10 .~
or 20 times -that in the case of the conven-tional methods~ - .:
with the consequence that the electrolysis r~-te can be -"' .: . .; . .................................... .
.. , .. , , . ., . , ~ ~, .
486~
greatly enhc~ncecl~ Furthermore, the ope.ra-tion can be carried out continuously, since -the feecling of the starting ma-terial and th~ recover;y of the resu].tan~t grown particles of pure metai can be carri.ed out in a continuous manner. Again, it 5 is possible -to employ an electro].y-tic cell of the closed typeO Hence, there is -the advantage that the dlssipation of a mist of the electrolytic solution that occurs in the case of the conventional methods can be prevented. All metals usable in the conventional hydroelectrometallurgy 10 can be applied to the new method, and good results are ~:
obtainedO More specifically, the metals exhibiting a :~
standard electrode potential exceeding -1 volt (at 25Co ) ., such as zinc, iron, cobalt, nickel, tin, lead and copper ~ ~
-., are applicable to the new method. ~.
In the aforementioned patent there is described :. :
an electrolytic cell that can be used in practicing the new methodO Figo 2 accompanying said patent s~ows a side ~:.
view in section illustrating one embodiment ~ an electroly~
tic cellO ~his electrolytic cell comprises an upper anode :~
. .
20 zone including a horizontal anode and a lower cathode zone including a horizontal cathode and is fixed on a base frame .
on which vibration generators are mounted to give a com-posite vibration to the whole cell and the seed par-ticles in the electrolyte thereby causing said par-ticles to collide 25 with the cathodeO ~his composite vibration consists of a :;
horizontal oscillation and an up-and-down vibration in the vertical planeO In order to generate this composite vibra- .
tion, .there is used an oscillating mechanism comprising two or more eccentric cams, transmission means, reducing gears ~''.
- 4 - :~
- ..
.. :: . .
, . - . ~ ~ . ~ ; ' .
.. .,. , ., ,, . ~ . . , . :. . . .
10~ 0 and a drivi.ng motor, ancl a vibrator for generatin~ a ver-: tic.~l vibration. I'hus, there i5 the clrawback tha-t substan- :~
tiall~ compli.ca-ted vibrating de~ices are required in the ~ ?
case of this electrolytic cell. EIence, an improved elec-trolytic cell free of such a drawback is desireda ~he obaect of the present invention is therefore . ;-to provide an improved electrolytic cell that can be used el-.ecti-~ely as an electrolytic cell in the new hydroelec~
trometallurgical method disclosed in the aforementioned patent. ;
- According to the present invention, there is provided an improved electrolytic cell for use in the - continuous hydroelectrometallurgical production of a metal : -by the electrolytic deposition of the metal on the surface .~
f suspended seed particles of pUIe metal comprising ~-(a) a vertical cylindrical cell comprising an upper anode zone including a horizontal anode and a lower cathode zone .
including a horizontal network cathode, said network cathode ~`.:..:..
partitioning the cathode zone into an upper and a lower part, (b) a stirrer positioned below said network cathode for . .
agitating the electrolyte to maintain said seed particles,~
contained therein in a suspended state within said cathode .;~
zone~
25 ~ (c) an inlet for charging into the cathode zone -the elec~
trolyte and the seed particl:es on which surface the metal :-~
is to be electrolytically deposited from the electrolyte, (d) an outlet for discharging the spent electrolyte from the anode zone, .
- 5 - :
.
. . .
(e) an ou-tlet for discharging and recovering from the cathode zone the enlarged metal particles which have grown as a result of the hereinbefore-described electrolytic deposition of the metal on the surface of the seed particles, and (f) means for passing an electric current between the anode and the cathode~
~ he most important ~eature of the electrolytic cell of the present invention resides in the fact that it possesses a horizontal network c~thode by which the cathode zone is partitioned into an upper and a lower par-t and, furthermore, there is provided a stirrer below said network cathode. Notwithstanding such a relatively simple setup, ;
in the case of the vertical cylindrical electrolytic cell ~
of this invention the seed particles, as a result of the ~-conjoint action of the network cathode and the stirrer9 are maintained in a stable state of suspension in the elec~
trolyte and by their collision with the cathode become -electronegatively charged. Hence, the electrolysis is carried out very effectively.
Preferred embodiments of the invention electroly-tic cell will be more fully described below by reference to the accompanying drawing, which is a side view in section illustrating one of such embodiments.
In the figure the reference numeral 1 indicates the vertical cylindrical elec-trolytic cell in its entirety~
in which upper anode zone 3 there is provided a horizontal anode 5, while its lower cathode zone 4 is provided with a -~
horizontal network cathode 6. ~he network cathode 6 is positioned a-t a midpoint relative to -the height of the cathode zone 6 ancl extends over t;he entire horizontal plane of the cathode zone thereby parti.tioning -the cathode zone in-to an upper part 11 and a lower pa:rt lOo In the lower part 10 below the network cathode -there is provided a stir-rer 8 that is driven by a motor 7. I-t is also possibls to provide the motor 7 below the electrolytic cell. In carry- ~:
ing out the electrolysis~ the seed particles 9 and elec- :
trolyte 12 are continuously fed -to the lower part of the ~;
cathode from an inlet 13, and the seed particles are kept in suspension in the electrolyte by -the rotation of the stirrer 8 to become dispersed inside the lower part 10 and upper part 11 of the cathode zo.ne. While the seed particles present in the lower part 10 are in a sta-te of intense ..
agitation as a result of being directly subjected to the agitation of the stirrer, those seed particles that are ;~
present in the upper part 11 are held in a gentle state of . .
agitation as a result of being decelerated rheologically .~.~
by the physical resistance of the network cathodet with the s consequence that the suspension layer formed is stable and of relatively low height~ ~he suspended seed particles, ;
which consist of fine particles of a pure me-tal of the same class as that to be electrolytically deposited, collide with the network cathode and become alectronega-tively charged.
As a consequence, the electrolytic deposition of metal on the surface of the seed particles is set up in the upper part 11 of the cathode zone, with the consequence that the ~
particles gradually grow into coarse particlesO The grown ;
metal particles of increased size tend to gravita-te to the " '' . '. ., ' : ' : ''' .. ..
o lower part 10 of the c~thode zone. Hence, the grown par-ticles of the upper part 11 become replaced by the fine particles that are present in the lower part. The grown particles are continuously withdrawn from the bot-tom of the electrolytic cell via an outlet 17 and recovered. ~he fine ;~
particles and electrolyte that are discharged by entrainment in the grown particles are separated from the grown particles and can then be recycled to the cathode zone.
- The reference numeral 2 in the figure represents a water-permeable diaphragm, eOg., a diaphragm of a filter cloth or asbestos, or a water-impermeable diaphragm, e.g. -~ -an ion-exchange resin membrane. ~he hydroelectrometallurgy by electrowinning, iOe., electrolysis by employing as the electrol~te a solution in which a metal has been dissolved in advance in the form its ion, does not require a diaphragm In general, it is believed that the use of a diaphragm is `~
not preferred~ because it increases the electric resistance and thus increases the cell voltage between the two elec-trodes. Accordingly, in the methods~ only when the in-soluble residue containing impurities is formed on the anode and floats in the electrolyte is there used a dia-phragm to prevent such a floating residue from contaminating the pure metal deposited in the cathode zone. ~ I
In carrying out the electrolysis without the use of a diaphragm or with the use of a water-permeable dia-phragm, the spent electrolyte is discharged from an outlet 14 located at the upper part of the anode zone. ~he dis-charged electrolyte can, as required, be recycled to the cathode zone via the inlet 13 after i-ts purification7 In ;
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~L~6~861?
the case of electrorefinin~ in which a diaphragm is re quired, the anode itself can be the crude metal. Again, as disclosed in the aforer;~entioned patent, the electrolysis can be carried ou-t by causing the fine particles of the atarting crude material, i~e., fine particles of the crude metal or fine particles of metal sulfide and the electron carrier metal, suspended in the anode zone to become elec~
tropositively charged by their collision with the surface of -the anode. In this case, it is necessary to provide a ;;~
:: ,:
stirrer in the anode zone for achieving the suspension of the particles and their collision with the anode. In the electrolysis in which a water-impermeable diaphragm is used, an inlet 16 for feeding an anolyte into the anode zone must be provided in addition to the foregoing inlet 13. Further~
more, in addition to the foregoing outlet 14, an outlet 15 -, ~
must be provided for discharging the spent catholyte from the cathode zone.
-~:
While the setup of the invention electrolytic cell . .
has been described hereinabove, its preferred embodiment 20 will be more fully described belowO
. ~. .
~ here is imposed no restriction as to the size of the seed particles used, and the seed particles may be of any size that can be suspended in the electrolyte by stir~
ring~ However, the seed particles are preferably of small `
25 size, and usually seed particles of a size ranging from about ODO5 millimeter to about 2 millimeters are used~
In the case of the electrolytic cell of the `~
- - present invention, the network cathode 6, as can be ap-preciated from the description given above, is not adapted -,,`
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: :: . ' ~: ' ~6486(~ ;
for depositing on the surface thereof of the metal to be recovered but f~mc-tions -to impart an electronegative charge to the seed particles that collide therewith. As regards the material to be used for the cathode, a suitable metal is chosen in consideration of such factors as corrosion resistance, resistance to attrition and electroconductivity. -~
Usually, most to be preferred is the use of titanium. ~he size of the mesh of the cathode is suitably about 5 milli~
meters to about 10 millimeters as a rule. When the meshes are too small, the seed particles e,perience difficulty in migrating from the lower part 10 of -the cathode zone to its upper part llo On the other hand~ when the meshes are too large, the frequency of collision of the seed particles that are present in the upper part 11 with the network cathode declines, and satisfactory results cannot be obtained O ~ ~ ` ' - . .
The stirrer 8 is made of a nonconductive, cor- -rosion resistant materialO As the shape of the vane, one which can effect the uniform dispersion of the seed particles ~;
is chosen, it being preferably one not imparted a -twist but . . .
of a flat boardlike form. ~he size of the vane is usually ~ ;~
such that its length in the transverse direction extends almost to the side walls of the lower part 10 of the ca-thode zone and its upper edge reaches to within several milli-meters of the underside of the network cathode. ~he speed at which the stirrer is rotated is one which forms a rela- `
tively thin suspension layer of the seed particles, iOe., a suspension layer of relatively low height, in the upper part 11 of the cathode zone, i~eO, above the network cathode ~,.
: '` -; . , : . : .. . .
8~(~
In genercll, the thickness of the suspension layer is pre-ferably from about 1.0 centimeter to about 2 centimeters in the case of a small-size electrolytic cell. When the ëlec~
trolytic cell is of large scale~ the thickness of -the sus~
pension layer will vary somewhat. When the thickness of the suspension layer becomes too great, a decline takes place in the frequency with which the seed particles cel-lide with -the network cathode, with the conse~uence that ~ ~ -the number of particles becoming electronegatively charged decreases to cause a decline in the electrolytic efficiency.
The rotating speed of the stirrer for forming a suspension layer of the seed particles of a sui-table thickness above the network catho~e will vary in accordance with the size of the stirrer vane, the size and specifîc gravity of the seed particles, the size of the meshes of the cathode, the diameter o~ the electroly-tic cell, the amperage of the elec-. ~
tric current, etcO A suitable rotating speed can be de-termined by a preliminary test~ In general, this will bs ~-in the range of 50 - 1000 rpm.
The electrolytic cell, when viewed as a whole, has the shape of a vertical cylinder. ~he distance between the anode and cathode should be made as small as possible for reducing the electric resistance. Hence, the larger the scale of the electrolytic cell, the smaller the height to diameter ratioO ~hus, the cell becomes as a whole o~e ~` --having a cylindrical shape in which the height is less than the diameter. As can be appreciated from what has been described hereinbefore, the total surface area of the seed particles that are electronegatively charged by the collision : . : . ~ . .. . . . .
of the seed particles with the network cathode 6 is far greater than the surface area of the conventional cathode - plate~ Hence, the current density that can be applied Per unit area of the horizontal section of the cathode zone 4 is far greater than that of the conventional method. l'his is equally applicable in the case of the anode zone in the ~ -case of electrorefining~ which is carried out by suspending -fine particles of the starting ma'erial in the anode zone and causing the collision of said particles with the anodeO
However, in the case of electrowinning, i.e4, where the electrolysis is carried out by employing as the electrolyte a solution in which a metal has been dissolved in advance in the form of its ion, a suitable current density should ~ ;~
be applied in accordance with the surface area of the anode ~
used. In this case, usable is a cylindrical cell consist- ;
ing of an upper anode zone having a diameter which makes it possible to accomodate an anode having a surface area sui- ~
table for the electric current to be applied and a lower ~-cathode zone of a diameter smaller than that of the upper anode zoneO
As the electrolyte, those used in the conventional electrolytic processes can be used. The concentration of the metallic ions is usually at least few grams per liter ~ he most important feature of the in~ention elec-trol~tic cell, which has been fully described hereinbeforeas to its setup and method of operation, resides in the fact that it has made possible the suspension of seed particles in the cathode zone and the formation of a stable suspension layer of seed particles which collide with the cathode .
113 ~;~86~
above -the network cathode, this ha~ing been achieved by the oonjoint effec-ts of having made the electroly-tic cell in a horizontal cylindrical form, using a network cathode and the provision of a stirrer therebwlow. ~he setup of this electrolytic cell is exceedingly simple, and its operation is also very easyO In addition, a current of large amperage ;~
can be passed therethrough, and the electrolysis can be smoothly carried out continuously with high efficiency. l~ -The electrolytic cell described in the aforemtnioned patent, in which the seed particles are kept in suspension by oscil-lation, is of a complicated setup. Again~ in the case of ;
the conventional method in which the seed particles of the ~ ;
metal and the electrolyte were merely stirred with the ro~
tating vane, the following difficultiss were experienceO - ;~
When the speed of the rotating vane was increased, the -seed particles of the metal would be localized in the ` ~-~
vicinity of the inside wall of the electrolytic cell, owing to the strong centrifugal force acting on the seed particles. ;
On the other hand, when the speed of rotatio~ of the vane was reduced, it would be impossible to maintain the sus~
pension in a stable state. ~urther, when there is a change in, say, the specific gravity of the seed particles, their ;
particle size and amount charged, or the specific gra~ity -~
of the electrolyte and its viscosity, the adjustment be~
comes troublesome. However, in case of the present inven- ` ~;
tion, the tolerances with respect to the changes in -these factors is extremely broadO Hence, the present invention ~ ~
has made it possible to overcome the shortcomings of the ' ~''-'~!` `''^~' ' conventional methods. ~;
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~he f`ollowin~ exc~mples, while not intended to be limiting, will serve to further illustrate the present in-vention. In all the examples, an electrolytic cell of small :~
size was used, and for brevity experiments illustrating the case of electrowinning of copper were carried out. In these ~.
examples the experime.nts were carried out while varying the rotating speed of the stirrer, the size of the seed particles : and the cell current. As a consequence, it was found that when a stable suspension layer of the seed particles was formed above the network cathode and that when the thick-ness of this suspension layer was about 1 - 2 centimeters, and particularly about 1 - 105 centimeters, a most satisfac- :
tory current efficiency was achieved.
~.
Example 1 An electrolytic cell consisting of an upper anode ..
zone having a height of 10 centimeters and an inside diameter of 14 centimeters and including a copper anode of 1.5 square decimeters and a lower cathode zone having a height of 8 centimeters and an inside diameter of 6 centimeters and .:
including a network cathode m~de of a titanium lath and a :. ;~
stirrer therebelow was used. ~he size of the meshes of this `: ~:
cathode is 10 millimeters, and this cathode is installed at a height 205 centimeters from the bottom of the cell~ ~o .~
the shaft of the stirrer are fitted at the same height four ~.`
vanes having the dimensions in the lateral direction of 2~5 ~.
centimeters and in the vertical direction of 1.8 cen-timeters.
This electrolytic cell was filled with an electrolyte having ;
a concentration o~ 50 grams of Cu per liter and 100 grams of H2S04 per liter. This was followed by charging ~50 grams ~ "~;'`
':
~4860 ~ ~
of seed particles of pure copper of 32 - 48 Tyler mesh ~-size to the cathode zone. The electrolysis was then carried out a-t a temperature of room tempera-ture to 60C by passing a 5-ampere current between -the electrodes while operating the stirrer. Th-e thickness of the ,suspension layer of seed particles formed above the network cathode and the current efficiences with respect to the deposition of copper on the seed particles and the network cathode are sho~m in ~able 1, below.
,, Table 1 ._ . _ ~ _ _ - .
Thickness ofCurrent Efficiency (%) Speed of Stirrer Suspension Layer _ (rpm) (cm) ~ ~d ~rt'ol~ Cathode ~
35 1,0 96,6 ~0,01 ~ -403 1.1 96.1 0~08 499 1.5 95.3 002 i,~
15 - - _ -- ' 3 _ _ ~.7 -... - , .
, ",. ~ ~ ~
It can be appreci,~ted from this table that at a rotating speed of the stirrer of about 300 - 400 rpm there was formed a suspension layer having a thickness of about 1 ~, centimeter above the~cathode and that the current efficiency obtained ~as excellent, whereas when the rotating speed exceeded about 600 rpm, the thickness of the suspension layer became greater than about 2 centimeter and there was a slight decline in the amount of copper deposited on the seed particles, while there was an increase in the amount of copper deposi-ted on ~the cathode.
In this electrolysis lt was seen that the ' ~: , - , . . . . . . .
lOG48~iiO
suspenslon layer W95 stably obtain~d abo-ve the ne-twork cathode an~ that the particles in this suspension layer were circula-ting within the cell at a slow speed of about 40 - 120 rpm while colliding with each otherO
Example 2 An electrolytic ~ell of the same type as that used in Example 1 was employed, and the electrolysis was conduc-ted under identical conditions as in(~icated therein, except -that the particle size of the seed particles of copper was ~`
varied as shown in ~able 20 The optimum rotating speed of ;~ :
the stirrer, the thickness of the suspension layer above the network cathode, and the current efficiencies with ~-respect to the deposition of copper on seed particles and the network cathode are shown in ~able 2. :.
able 2 _ . ................... _ . .. .. .. , :
Size of seed Stirrer ~hickness of Current Efficiency (%) Particles Speed Suspension Seed (mesh) (rpm) (cm) Particles Cathode ~ :
_ ~ ___ "
32 - 48 35 102 96.6~ 0.01 ~ J`
70 - 80 39& 1.2 98020008 I100 - 150 38B 1.3 96030.09 :;
^~
It can be seen from these results that when the ~
rotating speed of the stirrer is about 300 - 400 rpm sus- :-pension layers having thicknesses of about 1 - 1.3 cen-ti-meters are formed, and that thus it is possible to carry out the electrolysis stably using copper powders of varying : :
particle siæe with practically no change in the rotating :
speed of -the stirrer, if the other conditions of the ~:
.:
il06~8~i0 ~
electrolysis are the same. ~ :
Example 3 -; The experiment was conduc-ted using an electrolytic cell of the seme type as that used in Example 1 but varying, as shown in Table 3, the cell ^urrent, and hence the current ~:
density per unit horizontal sectional area of the cathode ~ ; .
zoneO Seed particles of copper of 32 - 48 mesh size were ;
used in an amount of 350 grams~ Since the rise in the in- `
side temperature of the cell was excessive when the cell current was 10 amperes or higher, the electrolysis was carried out by cooling the electrolyte by circulating it through a separate cooling tank. The results obtained are shown in Table 3, belowO
Table 3 Cell Current I Electrolyte Tempera- - ¦ C
Current Density Circulation ture Speed Seed:
(amP) (ampidm ) ~ml/min.)_ ( CO) (rpm) Particles Cathode 17~8 _ 63~5 403 96~1 0.08 35 ~ 7 80 61~ 0 L~52 97 o 9 0 ~14 :71 ~4 ~ 250 60 o 5 500 99 ~4 0~ 14 107~1 250 67~5 6l7 9508 0~10 ; ~;
It can be seen from the results given in the forego~
ing table that it is possible to carry out the electrolysis : very e~fectively with an exceedingly high current density when the electrolytic cell of the present invention is used, and that at high current densities the rotating speed of the stirrer is preferably increased somewhat~
~ 17 _
This invention relates to an improved electrolytic cell for use in the continuous hydroelectrometallurgical production of a metal by the eleckrolytic deposition of the metal on the surface of suspended seed particles of the pure me~al.
Such a hydroelectrometallurgical method and appara-tus for use in such a method has been disclosed by me in United States Patent 3~787,293.
Hydroelectrometallurgy, as is well known, includes ~ ;
electrorsfining and electrowinning. While the former is a method which comprises carrying out an aqueous electrolysis by using a crude metal containing impurities as an anode thereby depositing a pure metal on a cathode, the latter is a method which comprises carrying out the electrolysis by employing as the electrolyte a solution in which a metal has been dissolved in advance in the foDm of its ion thereby depositing the metal on a cathode and thereafter recovering same.
A new method for carrying out the hydroelectrome-tallurgy has been fully described in the aforesaid United States Patent 3,787,293~
Such a method, in brief, comprises suspending particles of a starting crude metal or metal sulfide in the anode zone and seed particles of the pure metal in ~he cathode zone, causing said particules to collide with the surfaces of the anode and cathode, respectively, passing an electric current through said anode and cathode, the g~ .
. . . .
~0~ 8~
particles of -th~ cr-ude ~letal or ~letal sulfide ~eing electro-~ositively charged due to their collision with the anode and becoming dissolved in an electrolyte solution, the seed particles bein~ electronegatively charged due to -their collision wi-th the cathode, whereby the metal ions in the electrol-~te solution are cathodically deposited as the metal on said seed particles, and thereafter recovering from the cathode zone the enlarged metal particles which have grown as a result of said electrolytic deposi-tion of the metal on the seed particles In the conventional hy~roelectrometallur~ical ; methods an anode plate and a ca-thode plate were suspended perpendicularly in an electrolyte solution and by passing an electric current between the two electrodes the metal was deposited on the cathode plate, after which the cathode plate was pulled up from the electrolytic cell and the . ;-deposited metal was recoveredO In this case the current .-~
per square decimeter was restricted to about 2 - 5 amperes, and the operation was carried out in a batchwise mannerO :~
As compared with such conventional methods, the above~men- `
tioned new method possesses an exceedingly distinctive feature in that the pure me-tal is deposited on -the seed ;~
metal particles -that are kep-t in suspension in the cathode :
zone9 after which the grown metal particles are recovered.
Since the whole area of the suspended particles is ~ar - - ~
greater than that of an electrode plate, the electric cur- ~.
rent that can be applied is very great, say, more than 10 .~
or 20 times -that in the case of the conven-tional methods~ - .:
with the consequence that the electrolysis r~-te can be -"' .: . .; . .................................... .
.. , .. , , . ., . , ~ ~, .
486~
greatly enhc~ncecl~ Furthermore, the ope.ra-tion can be carried out continuously, since -the feecling of the starting ma-terial and th~ recover;y of the resu].tan~t grown particles of pure metai can be carri.ed out in a continuous manner. Again, it 5 is possible -to employ an electro].y-tic cell of the closed typeO Hence, there is -the advantage that the dlssipation of a mist of the electrolytic solution that occurs in the case of the conventional methods can be prevented. All metals usable in the conventional hydroelectrometallurgy 10 can be applied to the new method, and good results are ~:
obtainedO More specifically, the metals exhibiting a :~
standard electrode potential exceeding -1 volt (at 25Co ) ., such as zinc, iron, cobalt, nickel, tin, lead and copper ~ ~
-., are applicable to the new method. ~.
In the aforementioned patent there is described :. :
an electrolytic cell that can be used in practicing the new methodO Figo 2 accompanying said patent s~ows a side ~:.
view in section illustrating one embodiment ~ an electroly~
tic cellO ~his electrolytic cell comprises an upper anode :~
. .
20 zone including a horizontal anode and a lower cathode zone including a horizontal cathode and is fixed on a base frame .
on which vibration generators are mounted to give a com-posite vibration to the whole cell and the seed par-ticles in the electrolyte thereby causing said par-ticles to collide 25 with the cathodeO ~his composite vibration consists of a :;
horizontal oscillation and an up-and-down vibration in the vertical planeO In order to generate this composite vibra- .
tion, .there is used an oscillating mechanism comprising two or more eccentric cams, transmission means, reducing gears ~''.
- 4 - :~
- ..
.. :: . .
, . - . ~ ~ . ~ ; ' .
.. .,. , ., ,, . ~ . . , . :. . . .
10~ 0 and a drivi.ng motor, ancl a vibrator for generatin~ a ver-: tic.~l vibration. I'hus, there i5 the clrawback tha-t substan- :~
tiall~ compli.ca-ted vibrating de~ices are required in the ~ ?
case of this electrolytic cell. EIence, an improved elec-trolytic cell free of such a drawback is desireda ~he obaect of the present invention is therefore . ;-to provide an improved electrolytic cell that can be used el-.ecti-~ely as an electrolytic cell in the new hydroelec~
trometallurgical method disclosed in the aforementioned patent. ;
- According to the present invention, there is provided an improved electrolytic cell for use in the - continuous hydroelectrometallurgical production of a metal : -by the electrolytic deposition of the metal on the surface .~
f suspended seed particles of pUIe metal comprising ~-(a) a vertical cylindrical cell comprising an upper anode zone including a horizontal anode and a lower cathode zone .
including a horizontal network cathode, said network cathode ~`.:..:..
partitioning the cathode zone into an upper and a lower part, (b) a stirrer positioned below said network cathode for . .
agitating the electrolyte to maintain said seed particles,~
contained therein in a suspended state within said cathode .;~
zone~
25 ~ (c) an inlet for charging into the cathode zone -the elec~
trolyte and the seed particl:es on which surface the metal :-~
is to be electrolytically deposited from the electrolyte, (d) an outlet for discharging the spent electrolyte from the anode zone, .
- 5 - :
.
. . .
(e) an ou-tlet for discharging and recovering from the cathode zone the enlarged metal particles which have grown as a result of the hereinbefore-described electrolytic deposition of the metal on the surface of the seed particles, and (f) means for passing an electric current between the anode and the cathode~
~ he most important ~eature of the electrolytic cell of the present invention resides in the fact that it possesses a horizontal network c~thode by which the cathode zone is partitioned into an upper and a lower par-t and, furthermore, there is provided a stirrer below said network cathode. Notwithstanding such a relatively simple setup, ;
in the case of the vertical cylindrical electrolytic cell ~
of this invention the seed particles, as a result of the ~-conjoint action of the network cathode and the stirrer9 are maintained in a stable state of suspension in the elec~
trolyte and by their collision with the cathode become -electronegatively charged. Hence, the electrolysis is carried out very effectively.
Preferred embodiments of the invention electroly-tic cell will be more fully described below by reference to the accompanying drawing, which is a side view in section illustrating one of such embodiments.
In the figure the reference numeral 1 indicates the vertical cylindrical elec-trolytic cell in its entirety~
in which upper anode zone 3 there is provided a horizontal anode 5, while its lower cathode zone 4 is provided with a -~
horizontal network cathode 6. ~he network cathode 6 is positioned a-t a midpoint relative to -the height of the cathode zone 6 ancl extends over t;he entire horizontal plane of the cathode zone thereby parti.tioning -the cathode zone in-to an upper part 11 and a lower pa:rt lOo In the lower part 10 below the network cathode -there is provided a stir-rer 8 that is driven by a motor 7. I-t is also possibls to provide the motor 7 below the electrolytic cell. In carry- ~:
ing out the electrolysis~ the seed particles 9 and elec- :
trolyte 12 are continuously fed -to the lower part of the ~;
cathode from an inlet 13, and the seed particles are kept in suspension in the electrolyte by -the rotation of the stirrer 8 to become dispersed inside the lower part 10 and upper part 11 of the cathode zo.ne. While the seed particles present in the lower part 10 are in a sta-te of intense ..
agitation as a result of being directly subjected to the agitation of the stirrer, those seed particles that are ;~
present in the upper part 11 are held in a gentle state of . .
agitation as a result of being decelerated rheologically .~.~
by the physical resistance of the network cathodet with the s consequence that the suspension layer formed is stable and of relatively low height~ ~he suspended seed particles, ;
which consist of fine particles of a pure me-tal of the same class as that to be electrolytically deposited, collide with the network cathode and become alectronega-tively charged.
As a consequence, the electrolytic deposition of metal on the surface of the seed particles is set up in the upper part 11 of the cathode zone, with the consequence that the ~
particles gradually grow into coarse particlesO The grown ;
metal particles of increased size tend to gravita-te to the " '' . '. ., ' : ' : ''' .. ..
o lower part 10 of the c~thode zone. Hence, the grown par-ticles of the upper part 11 become replaced by the fine particles that are present in the lower part. The grown particles are continuously withdrawn from the bot-tom of the electrolytic cell via an outlet 17 and recovered. ~he fine ;~
particles and electrolyte that are discharged by entrainment in the grown particles are separated from the grown particles and can then be recycled to the cathode zone.
- The reference numeral 2 in the figure represents a water-permeable diaphragm, eOg., a diaphragm of a filter cloth or asbestos, or a water-impermeable diaphragm, e.g. -~ -an ion-exchange resin membrane. ~he hydroelectrometallurgy by electrowinning, iOe., electrolysis by employing as the electrol~te a solution in which a metal has been dissolved in advance in the form its ion, does not require a diaphragm In general, it is believed that the use of a diaphragm is `~
not preferred~ because it increases the electric resistance and thus increases the cell voltage between the two elec-trodes. Accordingly, in the methods~ only when the in-soluble residue containing impurities is formed on the anode and floats in the electrolyte is there used a dia-phragm to prevent such a floating residue from contaminating the pure metal deposited in the cathode zone. ~ I
In carrying out the electrolysis without the use of a diaphragm or with the use of a water-permeable dia-phragm, the spent electrolyte is discharged from an outlet 14 located at the upper part of the anode zone. ~he dis-charged electrolyte can, as required, be recycled to the cathode zone via the inlet 13 after i-ts purification7 In ;
,:
., . ~ , . .:
~L~6~861?
the case of electrorefinin~ in which a diaphragm is re quired, the anode itself can be the crude metal. Again, as disclosed in the aforer;~entioned patent, the electrolysis can be carried ou-t by causing the fine particles of the atarting crude material, i~e., fine particles of the crude metal or fine particles of metal sulfide and the electron carrier metal, suspended in the anode zone to become elec~
tropositively charged by their collision with the surface of -the anode. In this case, it is necessary to provide a ;;~
:: ,:
stirrer in the anode zone for achieving the suspension of the particles and their collision with the anode. In the electrolysis in which a water-impermeable diaphragm is used, an inlet 16 for feeding an anolyte into the anode zone must be provided in addition to the foregoing inlet 13. Further~
more, in addition to the foregoing outlet 14, an outlet 15 -, ~
must be provided for discharging the spent catholyte from the cathode zone.
-~:
While the setup of the invention electrolytic cell . .
has been described hereinabove, its preferred embodiment 20 will be more fully described belowO
. ~. .
~ here is imposed no restriction as to the size of the seed particles used, and the seed particles may be of any size that can be suspended in the electrolyte by stir~
ring~ However, the seed particles are preferably of small `
25 size, and usually seed particles of a size ranging from about ODO5 millimeter to about 2 millimeters are used~
In the case of the electrolytic cell of the `~
- - present invention, the network cathode 6, as can be ap-preciated from the description given above, is not adapted -,,`
_ g .- ' ' :-: ., ., . . : : :
~- .: .~ - . . ~ .
: :: . ' ~: ' ~6486(~ ;
for depositing on the surface thereof of the metal to be recovered but f~mc-tions -to impart an electronegative charge to the seed particles that collide therewith. As regards the material to be used for the cathode, a suitable metal is chosen in consideration of such factors as corrosion resistance, resistance to attrition and electroconductivity. -~
Usually, most to be preferred is the use of titanium. ~he size of the mesh of the cathode is suitably about 5 milli~
meters to about 10 millimeters as a rule. When the meshes are too small, the seed particles e,perience difficulty in migrating from the lower part 10 of -the cathode zone to its upper part llo On the other hand~ when the meshes are too large, the frequency of collision of the seed particles that are present in the upper part 11 with the network cathode declines, and satisfactory results cannot be obtained O ~ ~ ` ' - . .
The stirrer 8 is made of a nonconductive, cor- -rosion resistant materialO As the shape of the vane, one which can effect the uniform dispersion of the seed particles ~;
is chosen, it being preferably one not imparted a -twist but . . .
of a flat boardlike form. ~he size of the vane is usually ~ ;~
such that its length in the transverse direction extends almost to the side walls of the lower part 10 of the ca-thode zone and its upper edge reaches to within several milli-meters of the underside of the network cathode. ~he speed at which the stirrer is rotated is one which forms a rela- `
tively thin suspension layer of the seed particles, iOe., a suspension layer of relatively low height, in the upper part 11 of the cathode zone, i~eO, above the network cathode ~,.
: '` -; . , : . : .. . .
8~(~
In genercll, the thickness of the suspension layer is pre-ferably from about 1.0 centimeter to about 2 centimeters in the case of a small-size electrolytic cell. When the ëlec~
trolytic cell is of large scale~ the thickness of -the sus~
pension layer will vary somewhat. When the thickness of the suspension layer becomes too great, a decline takes place in the frequency with which the seed particles cel-lide with -the network cathode, with the conse~uence that ~ ~ -the number of particles becoming electronegatively charged decreases to cause a decline in the electrolytic efficiency.
The rotating speed of the stirrer for forming a suspension layer of the seed particles of a sui-table thickness above the network catho~e will vary in accordance with the size of the stirrer vane, the size and specifîc gravity of the seed particles, the size of the meshes of the cathode, the diameter o~ the electroly-tic cell, the amperage of the elec-. ~
tric current, etcO A suitable rotating speed can be de-termined by a preliminary test~ In general, this will bs ~-in the range of 50 - 1000 rpm.
The electrolytic cell, when viewed as a whole, has the shape of a vertical cylinder. ~he distance between the anode and cathode should be made as small as possible for reducing the electric resistance. Hence, the larger the scale of the electrolytic cell, the smaller the height to diameter ratioO ~hus, the cell becomes as a whole o~e ~` --having a cylindrical shape in which the height is less than the diameter. As can be appreciated from what has been described hereinbefore, the total surface area of the seed particles that are electronegatively charged by the collision : . : . ~ . .. . . . .
of the seed particles with the network cathode 6 is far greater than the surface area of the conventional cathode - plate~ Hence, the current density that can be applied Per unit area of the horizontal section of the cathode zone 4 is far greater than that of the conventional method. l'his is equally applicable in the case of the anode zone in the ~ -case of electrorefining~ which is carried out by suspending -fine particles of the starting ma'erial in the anode zone and causing the collision of said particles with the anodeO
However, in the case of electrowinning, i.e4, where the electrolysis is carried out by employing as the electrolyte a solution in which a metal has been dissolved in advance in the form of its ion, a suitable current density should ~ ;~
be applied in accordance with the surface area of the anode ~
used. In this case, usable is a cylindrical cell consist- ;
ing of an upper anode zone having a diameter which makes it possible to accomodate an anode having a surface area sui- ~
table for the electric current to be applied and a lower ~-cathode zone of a diameter smaller than that of the upper anode zoneO
As the electrolyte, those used in the conventional electrolytic processes can be used. The concentration of the metallic ions is usually at least few grams per liter ~ he most important feature of the in~ention elec-trol~tic cell, which has been fully described hereinbeforeas to its setup and method of operation, resides in the fact that it has made possible the suspension of seed particles in the cathode zone and the formation of a stable suspension layer of seed particles which collide with the cathode .
113 ~;~86~
above -the network cathode, this ha~ing been achieved by the oonjoint effec-ts of having made the electroly-tic cell in a horizontal cylindrical form, using a network cathode and the provision of a stirrer therebwlow. ~he setup of this electrolytic cell is exceedingly simple, and its operation is also very easyO In addition, a current of large amperage ;~
can be passed therethrough, and the electrolysis can be smoothly carried out continuously with high efficiency. l~ -The electrolytic cell described in the aforemtnioned patent, in which the seed particles are kept in suspension by oscil-lation, is of a complicated setup. Again~ in the case of ;
the conventional method in which the seed particles of the ~ ;
metal and the electrolyte were merely stirred with the ro~
tating vane, the following difficultiss were experienceO - ;~
When the speed of the rotating vane was increased, the -seed particles of the metal would be localized in the ` ~-~
vicinity of the inside wall of the electrolytic cell, owing to the strong centrifugal force acting on the seed particles. ;
On the other hand, when the speed of rotatio~ of the vane was reduced, it would be impossible to maintain the sus~
pension in a stable state. ~urther, when there is a change in, say, the specific gravity of the seed particles, their ;
particle size and amount charged, or the specific gra~ity -~
of the electrolyte and its viscosity, the adjustment be~
comes troublesome. However, in case of the present inven- ` ~;
tion, the tolerances with respect to the changes in -these factors is extremely broadO Hence, the present invention ~ ~
has made it possible to overcome the shortcomings of the ' ~''-'~!` `''^~' ' conventional methods. ~;
::
.. . .
~he f`ollowin~ exc~mples, while not intended to be limiting, will serve to further illustrate the present in-vention. In all the examples, an electrolytic cell of small :~
size was used, and for brevity experiments illustrating the case of electrowinning of copper were carried out. In these ~.
examples the experime.nts were carried out while varying the rotating speed of the stirrer, the size of the seed particles : and the cell current. As a consequence, it was found that when a stable suspension layer of the seed particles was formed above the network cathode and that when the thick-ness of this suspension layer was about 1 - 2 centimeters, and particularly about 1 - 105 centimeters, a most satisfac- :
tory current efficiency was achieved.
~.
Example 1 An electrolytic cell consisting of an upper anode ..
zone having a height of 10 centimeters and an inside diameter of 14 centimeters and including a copper anode of 1.5 square decimeters and a lower cathode zone having a height of 8 centimeters and an inside diameter of 6 centimeters and .:
including a network cathode m~de of a titanium lath and a :. ;~
stirrer therebelow was used. ~he size of the meshes of this `: ~:
cathode is 10 millimeters, and this cathode is installed at a height 205 centimeters from the bottom of the cell~ ~o .~
the shaft of the stirrer are fitted at the same height four ~.`
vanes having the dimensions in the lateral direction of 2~5 ~.
centimeters and in the vertical direction of 1.8 cen-timeters.
This electrolytic cell was filled with an electrolyte having ;
a concentration o~ 50 grams of Cu per liter and 100 grams of H2S04 per liter. This was followed by charging ~50 grams ~ "~;'`
':
~4860 ~ ~
of seed particles of pure copper of 32 - 48 Tyler mesh ~-size to the cathode zone. The electrolysis was then carried out a-t a temperature of room tempera-ture to 60C by passing a 5-ampere current between -the electrodes while operating the stirrer. Th-e thickness of the ,suspension layer of seed particles formed above the network cathode and the current efficiences with respect to the deposition of copper on the seed particles and the network cathode are sho~m in ~able 1, below.
,, Table 1 ._ . _ ~ _ _ - .
Thickness ofCurrent Efficiency (%) Speed of Stirrer Suspension Layer _ (rpm) (cm) ~ ~d ~rt'ol~ Cathode ~
35 1,0 96,6 ~0,01 ~ -403 1.1 96.1 0~08 499 1.5 95.3 002 i,~
15 - - _ -- ' 3 _ _ ~.7 -... - , .
, ",. ~ ~ ~
It can be appreci,~ted from this table that at a rotating speed of the stirrer of about 300 - 400 rpm there was formed a suspension layer having a thickness of about 1 ~, centimeter above the~cathode and that the current efficiency obtained ~as excellent, whereas when the rotating speed exceeded about 600 rpm, the thickness of the suspension layer became greater than about 2 centimeter and there was a slight decline in the amount of copper deposited on the seed particles, while there was an increase in the amount of copper deposi-ted on ~the cathode.
In this electrolysis lt was seen that the ' ~: , - , . . . . . . .
lOG48~iiO
suspenslon layer W95 stably obtain~d abo-ve the ne-twork cathode an~ that the particles in this suspension layer were circula-ting within the cell at a slow speed of about 40 - 120 rpm while colliding with each otherO
Example 2 An electrolytic ~ell of the same type as that used in Example 1 was employed, and the electrolysis was conduc-ted under identical conditions as in(~icated therein, except -that the particle size of the seed particles of copper was ~`
varied as shown in ~able 20 The optimum rotating speed of ;~ :
the stirrer, the thickness of the suspension layer above the network cathode, and the current efficiencies with ~-respect to the deposition of copper on seed particles and the network cathode are shown in ~able 2. :.
able 2 _ . ................... _ . .. .. .. , :
Size of seed Stirrer ~hickness of Current Efficiency (%) Particles Speed Suspension Seed (mesh) (rpm) (cm) Particles Cathode ~ :
_ ~ ___ "
32 - 48 35 102 96.6~ 0.01 ~ J`
70 - 80 39& 1.2 98020008 I100 - 150 38B 1.3 96030.09 :;
^~
It can be seen from these results that when the ~
rotating speed of the stirrer is about 300 - 400 rpm sus- :-pension layers having thicknesses of about 1 - 1.3 cen-ti-meters are formed, and that thus it is possible to carry out the electrolysis stably using copper powders of varying : :
particle siæe with practically no change in the rotating :
speed of -the stirrer, if the other conditions of the ~:
.:
il06~8~i0 ~
electrolysis are the same. ~ :
Example 3 -; The experiment was conduc-ted using an electrolytic cell of the seme type as that used in Example 1 but varying, as shown in Table 3, the cell ^urrent, and hence the current ~:
density per unit horizontal sectional area of the cathode ~ ; .
zoneO Seed particles of copper of 32 - 48 mesh size were ;
used in an amount of 350 grams~ Since the rise in the in- `
side temperature of the cell was excessive when the cell current was 10 amperes or higher, the electrolysis was carried out by cooling the electrolyte by circulating it through a separate cooling tank. The results obtained are shown in Table 3, belowO
Table 3 Cell Current I Electrolyte Tempera- - ¦ C
Current Density Circulation ture Speed Seed:
(amP) (ampidm ) ~ml/min.)_ ( CO) (rpm) Particles Cathode 17~8 _ 63~5 403 96~1 0.08 35 ~ 7 80 61~ 0 L~52 97 o 9 0 ~14 :71 ~4 ~ 250 60 o 5 500 99 ~4 0~ 14 107~1 250 67~5 6l7 9508 0~10 ; ~;
It can be seen from the results given in the forego~
ing table that it is possible to carry out the electrolysis : very e~fectively with an exceedingly high current density when the electrolytic cell of the present invention is used, and that at high current densities the rotating speed of the stirrer is preferably increased somewhat~
~ 17 _
Claims (4)
1. An electrolytic cell for use in the continuous hydroelectrometallurgical production of a metal by the electrolytic deposition of the metal on the surface of suspended seed particles of pure metal comprising (a) a vertical cylindrical cell comprising an upper anode zone including a horizontal anode and a lower cathode zone including a horizontal network cathode, said network cathode partitioning the cathode zone into an upper and a lower part, (b) a stirrer disposed below said network cathode for agitating the electrolyte to maintain the seed particles contained therein in a suspended state within said cathode zone, (c) an inlet for charging into the cathode zone the elec-trolyte and the seed particles on which surface the metal is to be electrolytically deposited from the electrolyte, (d) an outlet for discharging from the anode zone the spent electrolyte, (e) an outlet for discharging and recovering from the cathode zone the enlarged metal particles which have grown by the aforesaid electrolytic deposition of the metal on the surface of the seed particles, and (f) means for passing an electric current between the anode and the network cathode.
2. An electrolytic cell of claim 1 which further includes a diaphragm that separates said upper anode zone from said lower cathode zone.
3. An electrolytic cell of claim 2 which further includes in said anode zone a stirrer for agitating the electrolyte to maintain the fine particles of a starting crude material contained therein in a suspended state within said anode zone.
4. An electrolytic cell of claim 3 wherein said dia-phragm is a water-impermeable diaphragm and which further includes an inlet for charging the anolyte to the anode zone and an outlet for discharging the spent catholyte from the cathode zone.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50117146A JPS5241103A (en) | 1975-09-30 | 1975-09-30 | Equipment for electrolysis of metal suspension |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1064860A true CA1064860A (en) | 1979-10-23 |
Family
ID=14704589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA262,290A Expired CA1064860A (en) | 1975-09-30 | 1976-09-29 | Electrolytic cell for use in hydroelectrometallurgy |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4032425A (en) |
| JP (1) | JPS5241103A (en) |
| CA (1) | CA1064860A (en) |
| DE (1) | DE2644199A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1062651A (en) * | 1976-05-11 | 1979-09-18 | Anthony P. Holko | Process and apparatus for electrowinning metal from metal bearing solutions |
| US4244795A (en) * | 1978-05-24 | 1981-01-13 | Akzo N.V. | Process and apparatus for electrolytically removing metal ions from a solution thereof |
| FR2446669A1 (en) * | 1979-01-17 | 1980-08-14 | Bienvenu Gerard | METHOD AND DEVICE FOR IMPLEMENTING TRANSFERS OF MATERIAL OF PHYSICAL AND / OR CHEMICAL REACTIONS OR OF THERMAL TRANSFERS IN A FLUID MEDIUM |
| GB8508726D0 (en) * | 1985-04-03 | 1985-05-09 | Goodridge F | Purifying mixed-cation electrolyte |
| US4824541A (en) * | 1986-09-25 | 1989-04-25 | Shell Internationale Research Maatschappij B.V. | Fluid bed electrolysis cell |
| FR2606795B1 (en) * | 1986-11-17 | 1990-12-21 | Martineau Ets | METAL RECOVERY CELL |
| GB8900557D0 (en) * | 1989-01-11 | 1989-03-08 | Atomic Energy Authority Uk | Electrochemical cell |
| NL9001199A (en) * | 1990-05-23 | 1991-12-16 | Stork Screens Bv | CHARGING METHOD FOR ZINC SUSPENSION ACCUMULATOR; ZINC SUSPENSION ACCUMULATOR AND ZINC SUSPENSION TO BE USED FOR ACCUMULATOR. |
| US5318675A (en) * | 1993-07-20 | 1994-06-07 | Patterson James A | Method for electrolysis of water to form metal hydride |
| BRPI0604307B1 (en) * | 2006-07-12 | 2015-10-20 | Duberlis Correa Peña Y Lillo | electrohydrometallurgical process in alkaline medium for zinc extraction of electric furnace powder |
| US8877032B2 (en) | 2009-11-02 | 2014-11-04 | Dan Prokop | Generation of chemical reagents for various process functions utilizing an agitated liquid and electrically conductive environment and an electro chemical cell |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1225052A (en) * | 1915-12-31 | 1917-05-08 | Chem Ind Basel | Process of treating organic compounds by electrolysis. |
| US2099290A (en) * | 1932-02-04 | 1937-11-16 | Smith Corp A O | Apparatus for the manufacture of mercury sulphate |
| US2427433A (en) * | 1944-04-29 | 1947-09-16 | Nat Carbon Co Inc | Electrolytic processes |
| DE2105038C3 (en) * | 1970-02-03 | 1974-01-03 | Kawada, Tomoyoshi, Tokio | Method and device for direct electrodeposition of metals |
| US3787293A (en) * | 1971-02-03 | 1974-01-22 | Nat Res Inst Metals | Method for hydroelectrometallurgy |
| US3788965A (en) * | 1972-04-07 | 1974-01-29 | 2C 2B Corp | Hydrometallurgical solubilizer with selective electroplating mechanism |
| JPS5234390B2 (en) * | 1972-08-08 | 1977-09-02 | ||
| JPS5335883B2 (en) * | 1973-01-18 | 1978-09-29 |
-
1975
- 1975-09-30 JP JP50117146A patent/JPS5241103A/en active Granted
-
1976
- 1976-09-27 US US05/726,956 patent/US4032425A/en not_active Expired - Lifetime
- 1976-09-29 CA CA262,290A patent/CA1064860A/en not_active Expired
- 1976-09-30 DE DE19762644199 patent/DE2644199A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE2644199A1 (en) | 1977-04-14 |
| JPS551995B2 (en) | 1980-01-17 |
| JPS5241103A (en) | 1977-03-30 |
| US4032425A (en) | 1977-06-28 |
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