CA1335435C - Drum electrolysis - Google Patents
Drum electrolysisInfo
- Publication number
- CA1335435C CA1335435C CA000567777A CA567777A CA1335435C CA 1335435 C CA1335435 C CA 1335435C CA 000567777 A CA000567777 A CA 000567777A CA 567777 A CA567777 A CA 567777A CA 1335435 C CA1335435 C CA 1335435C
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- CA
- Canada
- Prior art keywords
- cathode
- drum
- metal
- electrolyte
- anode
- 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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of 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
- C25C7/002—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least an electrode made of particles
-
- 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
- C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
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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)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Discharge Heating (AREA)
Abstract
Disclosed are a process and an apparatus for electrolytically producing a metal from a liquid electrolyte containing a compound of the metal. The apparatus comprises a rotatable cathode drum and an anode inside the cathode. The cathode drum contains therein the electrolyte and a particulate material which is insoluble in the electrolyte under conditions of the electrolysis and is freely movable in the rotatable drum. By this way, the produced metal deposits inside the rotatable drum, typically on the particulate material, not on an inner surface of the drum. The particulate material is preferably a metal, especially the same metal as the metal produced by the electrolysis.
Description
DRUM ELECTROLYSIS
The present invention concerns an electrolysis process using a movable electrode in addition to one loose and freely moving solid medium present in the electrode, and a device or apparatus adapted for performing the process.
It is previously known to perform electrolysis using a mo-.Jc~l le, ~ove blc cathode, but in such electrolysis, a fastened material grows on the electrode (the cathode), and with time they will become useless unless separated metal is removed, for instance manually or in an automatical mechanical manner. Thus there has previously been performed electrolysis using a cylindrical rotating cathode where the separated metal is adhering on the outside of the electrode, and must be intermittently removed so that the electrode will not become useless.
If the anode in such electrolysis is placed inside the rotatable, for instance cylindrical, cathode, it might be expected that the cathode gradually would grow solid and become useless due to the deposited metal.
It has, however, surprisingly been found that this does not occur if there is a freely movable solid medium inside the cathode drum. Such a freely movable medium may inter alia comprise metal particles or spheres of the same metal as in the electrolyte, or of another conducting or non-conducting or inert material. By rotating the cathode, the particles thus "polish" the inner surface of the cathode drum, and at the same time the distance between the anode and the spheres will be less than between the anode and the cathode drum.
133543~
The present invention concerns an electrolysis process using a movable electrode in addition to one loose and freely moving solid medium present in the electrode, and a device or apparatus adapted for performing the process.
It is previously known to perform electrolysis using a mo-.Jc~l le, ~ove blc cathode, but in such electrolysis, a fastened material grows on the electrode (the cathode), and with time they will become useless unless separated metal is removed, for instance manually or in an automatical mechanical manner. Thus there has previously been performed electrolysis using a cylindrical rotating cathode where the separated metal is adhering on the outside of the electrode, and must be intermittently removed so that the electrode will not become useless.
If the anode in such electrolysis is placed inside the rotatable, for instance cylindrical, cathode, it might be expected that the cathode gradually would grow solid and become useless due to the deposited metal.
It has, however, surprisingly been found that this does not occur if there is a freely movable solid medium inside the cathode drum. Such a freely movable medium may inter alia comprise metal particles or spheres of the same metal as in the electrolyte, or of another conducting or non-conducting or inert material. By rotating the cathode, the particles thus "polish" the inner surface of the cathode drum, and at the same time the distance between the anode and the spheres will be less than between the anode and the cathode drum.
133543~
2 ~ 22813-45 By uslng such a process and an apparatus for electroly-sls, a produced metal deposlts lnslde the cathode drum but not on the cathode surface.
Thus, one aspect of the present lnventlon provldes an electrolysls process for electrolytlcally produclng a metal from a compound of the metal, whlch comprlses:
applylng an electrlc current through a cathode, a llquld electrolyte contalnlng the compound of the metal and an anode, whereln:
the cathode ls a rotatable drum rotatlng ln operatlon and contalns thereln the electrolyte;
the anode ls a rod extendlng between two ends of the cathode drum lnslde the cathode drum and comprlslng a plurallty of electrlcally conductlve anode plates each hanglng down lnto the electrolyte from the anode rod, the anode belng electrlcally lnsulated from the cathode drum other than through the anode plates and the electrolyte whlch ls ln contact wlth the cathode;
the rotatable drum further contalns thereln at least ln an lnltlal stage of the electrolysls an electrlcally conductlve partlculate materlal whlch ls insoluble ln the electrolyte under condltlons of the electrolysls and ls freely movable ln the rotatable drum to pollsh an inner surface of the rotatable drum, whereby the electrolytically produced metal deposlts on the electrlcally conductlve partlculate materlal lnslde the rotatable drum but not on the lnner surface thereof;
the partlculate lnsoluble materlal ls contlnuously supplled lnto and removed from the rotatable drum cathode; and the electrolyte ls contlnuously added lnto the rotatable drum cathode through one end and 18 contlnuously removed from the rotatable drum cathode through the opposlte end.
In a preferred embodlment, the plurallty of the electrlcally conductlve anode plates have such a shape that a llne drawn by connectlng lower edges thereof ls substantlally parallel wlth the surface of a bed formed of the electrlcally conductlve partlculate materlal.
In another preferred embodlment, the electrlcally conductlve partlculate materlal has a slze of from 3 to 10 mm.
A second aspect of the present lnventlon provldes an apparatus adapted for performlng the electrolysls process as deflned above, whlch comprlses:
a cathode ln the form of a drum whlch ls rotatable about a substantlally horlzontal axls and ls connected to a current source, the drum comprlslng a body and two end walls each havlng a central orlflce whlch ls provlded wlth means for supportlng an anode and the drum belng deslgned for contalnlng thereln a llquld electrolyte contalnlng a compound of the metal;
an anode whlch ls a rod extendlng between the two end walls of the cathode drum lnslde the cathode drum and comprising a plurality of electrlcalIy conductlve anode plates each hanglng down lnto the electrolyte from the anode rod, the anode belng electrlcally lnsulated from the cathode other than through the anode plates and the electrolyte whlch ls ln contact wlth the cathode;
means for supplylng the electrolyte; and means for dralnlng the electrolyte after use;
whereln the apparatus ls deslgned such that the cathode ~ 4 13354~ 22813-45 is capable of contalnlng thereln an electrlcally conductlve partlculate materlal which ls lnsoluble ln the electrolyte under condltlons of the electrolysls and ls freely movable ln the rotatable drum to pollsh an lnner surface of the rotatable drum and that the metal electrolytlcally produced deposlts onto the electrlcally conductlve partlculate materlal.
The freely movable solld medlum lnslde the cathode drum does not necessarlly have to be round or spherlcal, but can have any shape whlch accompllshes the above mentloned effects, and whlch rnakeR the metal deposlt on the partlcle surface of the medlum.
By contlnuously supplylng lnto the rotatable cathode an electrolyte, optlonally contalnlng free partlcles of the solld medlum, and, by contlnuously dralnlng poor electrolyte from the opposlte end of the cathode, metal partlcles or sllt may be contlnuously produced wlthout the cathode drum growlng solld.
Thls makes lt easy to remove a posslbly harmful or lnterferlng gas whlch has been produced durlng the electrolysls, by equlpplng the electrolysls drum wlth means for removlng the gas, such as an outlet or a fan for such gas whlch lt may be advlsable or necessary to store.
Examples of an apparatus sultable for performlng the above descrlbed electrolysls process wlll be herelnunder descrlbed by reference to the attached drawlngs, ln whlch:
Flg. 1 ls a sectlonal slde vlew of an embodlment of the apparatus havlng a cathode drum wlth anode dlscs thereln reachlng down lnto the electrolyte.
Flg. 2 ls a sectlonal vlew of the apparatus shown ln 4a 22813-45 Fig. l, but wlth marked roll bearlngs.
Flg. 3 ls a sectlonal slde vlew of a slmllar apparatus havlng a drum cathode slmllar to that shown ln Flg. 1, but the anode comprlses a tube wlth holes for addlng and dlscharglng electrolyte and gasses.
Flg. 4 ls a sectlonal slde vlew of another slmllar apparatus havlng a cathode drum, where the drum ls placed o~liquely for sultable sedlmentatlon of the partlcle materlal, and where the anode tube 18 surrounded by a non-conductlng sheet for reflnlng electrolysls.
In the apparatus sultable for performlng the electrolysls accordlng to the present lnventlon shown ln Flg. 1 and 2, the rotatlng cathode drum l wlth electrlcally lnsulated end plates 2 ls suspended on roll bearlngs 3. The penetratlng anode comprlses an electrlcally conductlve anode rod 4 wlth anode plates 5, preferably made of lead or some other sultable materlal, hanglng down lnto the electrolyte. The anode rod ls connected to a posltlve termlnal of a current source ~not shown). The freely movable, partlculate medlum lnslde the rotatlng cathode drum 1 mounted on a rotatable end ls glven by the reference number 7.
The partlcle materlal does not have any dlrect contact wlth the anode plate 5. The shape of the anode plates ls such that a llne formed by connectlng lower edges of the plates ls substantlally parallel wlth the surface of a bed formed of the partlculate medlum. Inslde the cathode drum 1, there ls an electrolyte 8, whlch may be dralned, optlonally together wlth produced sllt and/or waste materlal, through a dralnage openlng 10, where the electrolyte whlch ls dralned at lO ls poor ln the current catlon 4b ^ 22813-45 which 18 belng electrolysed. The electrolyte optlonally contalnlng the partlculate solld medlum, ls supplled through an openlng 9, and the drum cathode 1 ls connected at 11 to a negatlve termlnal of a current source (not shown) for example, through a slldlng connectlon. The dlrectlon of rotatlon of the cathode drum ls glven by outer arrows ln Flg. 2, and the movement of the partlculate medlum ls glven by lnner arrows ln Flg. 2.
In another posslble embodlment of the apparatus accordlng to the lnventlon, the slde walls 2 are removed, and the partlculate materlal may mlgrate towards the open ends of the cathode drum 1, and from there be taken out durlng rotatlon or shaklngJvlbratlng of the cathode drum.
A slmllar apparatus ls deplcted ln Flg. 3, where each part ls provlded wlth the same reference number as ln Flgs 1 and 2, but where the anode does not lnclude anode plates, but ls only a perforated tube and where the electrolyte solutlon stands ln dlrect contact wlth the tube 4. Thls apparatus makes lt slmple to remove produced gas through an openlng 10 by suctlon or blowlng.
Yet another slmllar apparatus for performlng the electrolysls process ls given in Fig. 4, whereln the anode tube 4 ls perforated here as well, but as mlddle anode sectlon 16-17 ls provlded wlth a non-conductlng cloth 18 and thls sectlon 14 has a separate supplylng condult 13 and an exlt condult 15 for the partlculate materlal, sllt and solutlon. For persons skllled in electrolysis lt would be obvlous that such an apparatus may be used for reflnlng of a metal or electrolysls where the so-called redox-palr are present, such as electrolysls of Cu(I) chlorlde solutlon ~cupro-solutlon) where Cu(II) chloride ls produced at the 133543~
4c ^ 22813-45 anode and may be sectioned through the cloth and out lnto the condult 15, separately from the exlt of the cathode chamber 10.
Produced gas, deplcted by bubbles ln the flgure, ls taken out through an outlet 12. Each reference number refers as well to the correspondlng elements ln the other flgures. The cathode drum shown ln Flg. 4, ls ln addltlon lncllned to produce sedlmentatlon of the partlculate medlum accordlng to partlcle slze, where large partlcles gather ln a lower part of the cathode drum and may therefrom easlly be remove.
Example for productlons of metal wlll be descrlbed herelnunder by uslng the process accordlng to the lnventlon.
Experiment 1:
- The purpose for this experiment was to determine the effect of the process according to the invention during production of metal, i.e. to determine whether metal did not deposit on the cathode walls but on the particulate material in the cathode drum only. The cathode drum (diameter = 20 cm, length = 100 cm, made of 316 L stainless steel) was filled with 4,00 kg Cu-spheres (so-called "prills") with a diameter of 3 - 5 mm, and approx. 9 1 electrolyte.
(Intervals within which the particular general trial parameters lie, are: H2SO4 - 50-200 g/l, metal concen-tration - 5-60 g/l in the inlet, temperature - 25-30C up to 70-80 C, metal cations - Cu2 , Ni2 , Zn , current density - 50-2000 A/m2, rotation of the cathode drum -1-20 rpm (corresponding to 1-20 cm/sec. periperally), weight of solid medium - 1-10 kg (corresponding to 100-1000 kg/m ).) The anode comprised in this trial 19 Lead anode plates with a mutual distance of S cm inside the cathode drum. The electrolysis device was mounted on rolls, and a variable motor rotated the drum with 17 rpm while the anode was stationary. The device was heated by help of heating cables placed around the drum (2 x 400 W) and received their energy via two sliding contacts of 220 V. A contact thermostate regulated the temperature with 5 C accuracy.
The positive end of a rectifier was connected to the anode rod which protruded from openings in the end walls of the cathode drum. The negative pole was connected to a S mm lead plate which slided against the rotating cylinder and was kept in place by a spring which gave good contact without tendencies to spark production. The system could withstand 200 A. Electrolyte was supplied 133S43~
through the one end of the cathode drum, and drained from the other end. Current was supplied when the working temperature was reached while the drum rotated continously.
Continous repacement of the particulate medium was not performed in this experiment, and the particles were allowed to grow. The experiment was done for 9~ hours at 25-28C by using 60 A. This gave a current density of 240 A/m2 at a cell voltage of 2,8 V.
The results of the experiment are given in Table l. By these operating conditions there was produced 0,3 kg copper deposited on the copper spheres in the solid medium in the cathode drum only. The drum walls per se were com-pletely free from copper deposits.
Table l.
2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 3,3 g/l 44 g/l 9,6 l/h Drained 0,l g/l 92 g/l 9,6 l/h 28C
During the experiment there was also produced hydrogen, but this was effectively removed by suction. The trial shows that metal is deposited on the solid medium only.
Experiment 2:
The same prcedure as in experiment l was used, but with increased temeperature and a supply to the cell of 32 g/l copper and a drainage from the cell of 5 g/l copper to determine whether the solid medium (the copper spheres, "prills") still were produced at increased copper concen-trations without deposits of copper on the drum walls at 50C. The results are given in Table 2. ~t the trials, the cell voltage = 2,4 V, Current density = 240 A/m , - ~7~ 133543S
Duration = 37 hours, Current efficiency = 70%. There was produced 1,8 kg metal on the solid medium alone.
5 Table 2:
2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 32,0 g/l 176 g/l 1,74 l/h Drained 5-7 g/l 260- 1,41 l/h 50 C
270 g/l Experiment 3:
The same procedure as in experiment 1 was used, except that this experiment was a copy of a true electro extraction procedure for copper, where the feed electrolyte is approx.
60 g/l Cu and the drainage is 30-40 g/l Cu at 55-60C.
The operating conditions were: Cell voltage = 2,7 V, Current density = 240 A/m2, Duration = 18 hours, Current efficiency = 55% (on account of Fe3 ). There was at the trial produced 0,70 kg copper deposited on the medium material (the copper spheres) alone. The operating con-ditions are given in table 3. The trial shows that the process according to the invention may be used under usual conditions for electro production of metal.
Table 3. 2+ 3+ Electrolyte Cu Fe H2SO4 supply Temp.
Supplied the cell 58 g/l 2 g/l 64 g/l 1,5 l/h Drained 35 g/l 2 g/l 107 g/l 1,4 l/h 55-60 C
Experiment 4:
The same procedure as in experiment 1 was used, except that the current density was increased to 800 A/m , while the temperature was kept to 55-60C with a supply of 32 g/l Cu.
(The cell current = 200 A, no iron in the supplied material.) The operating conditions are given in table 4. There was __ -8- 1335 435 produced 0,66 kg copper which was deposited on the copper medium in the drum alone. The trial was performed with cell voltage = 3,3 V, Current density 800 A/m2, duration =
Thus, one aspect of the present lnventlon provldes an electrolysls process for electrolytlcally produclng a metal from a compound of the metal, whlch comprlses:
applylng an electrlc current through a cathode, a llquld electrolyte contalnlng the compound of the metal and an anode, whereln:
the cathode ls a rotatable drum rotatlng ln operatlon and contalns thereln the electrolyte;
the anode ls a rod extendlng between two ends of the cathode drum lnslde the cathode drum and comprlslng a plurallty of electrlcally conductlve anode plates each hanglng down lnto the electrolyte from the anode rod, the anode belng electrlcally lnsulated from the cathode drum other than through the anode plates and the electrolyte whlch ls ln contact wlth the cathode;
the rotatable drum further contalns thereln at least ln an lnltlal stage of the electrolysls an electrlcally conductlve partlculate materlal whlch ls insoluble ln the electrolyte under condltlons of the electrolysls and ls freely movable ln the rotatable drum to pollsh an inner surface of the rotatable drum, whereby the electrolytically produced metal deposlts on the electrlcally conductlve partlculate materlal lnslde the rotatable drum but not on the lnner surface thereof;
the partlculate lnsoluble materlal ls contlnuously supplled lnto and removed from the rotatable drum cathode; and the electrolyte ls contlnuously added lnto the rotatable drum cathode through one end and 18 contlnuously removed from the rotatable drum cathode through the opposlte end.
In a preferred embodlment, the plurallty of the electrlcally conductlve anode plates have such a shape that a llne drawn by connectlng lower edges thereof ls substantlally parallel wlth the surface of a bed formed of the electrlcally conductlve partlculate materlal.
In another preferred embodlment, the electrlcally conductlve partlculate materlal has a slze of from 3 to 10 mm.
A second aspect of the present lnventlon provldes an apparatus adapted for performlng the electrolysls process as deflned above, whlch comprlses:
a cathode ln the form of a drum whlch ls rotatable about a substantlally horlzontal axls and ls connected to a current source, the drum comprlslng a body and two end walls each havlng a central orlflce whlch ls provlded wlth means for supportlng an anode and the drum belng deslgned for contalnlng thereln a llquld electrolyte contalnlng a compound of the metal;
an anode whlch ls a rod extendlng between the two end walls of the cathode drum lnslde the cathode drum and comprising a plurality of electrlcalIy conductlve anode plates each hanglng down lnto the electrolyte from the anode rod, the anode belng electrlcally lnsulated from the cathode other than through the anode plates and the electrolyte whlch ls ln contact wlth the cathode;
means for supplylng the electrolyte; and means for dralnlng the electrolyte after use;
whereln the apparatus ls deslgned such that the cathode ~ 4 13354~ 22813-45 is capable of contalnlng thereln an electrlcally conductlve partlculate materlal which ls lnsoluble ln the electrolyte under condltlons of the electrolysls and ls freely movable ln the rotatable drum to pollsh an lnner surface of the rotatable drum and that the metal electrolytlcally produced deposlts onto the electrlcally conductlve partlculate materlal.
The freely movable solld medlum lnslde the cathode drum does not necessarlly have to be round or spherlcal, but can have any shape whlch accompllshes the above mentloned effects, and whlch rnakeR the metal deposlt on the partlcle surface of the medlum.
By contlnuously supplylng lnto the rotatable cathode an electrolyte, optlonally contalnlng free partlcles of the solld medlum, and, by contlnuously dralnlng poor electrolyte from the opposlte end of the cathode, metal partlcles or sllt may be contlnuously produced wlthout the cathode drum growlng solld.
Thls makes lt easy to remove a posslbly harmful or lnterferlng gas whlch has been produced durlng the electrolysls, by equlpplng the electrolysls drum wlth means for removlng the gas, such as an outlet or a fan for such gas whlch lt may be advlsable or necessary to store.
Examples of an apparatus sultable for performlng the above descrlbed electrolysls process wlll be herelnunder descrlbed by reference to the attached drawlngs, ln whlch:
Flg. 1 ls a sectlonal slde vlew of an embodlment of the apparatus havlng a cathode drum wlth anode dlscs thereln reachlng down lnto the electrolyte.
Flg. 2 ls a sectlonal vlew of the apparatus shown ln 4a 22813-45 Fig. l, but wlth marked roll bearlngs.
Flg. 3 ls a sectlonal slde vlew of a slmllar apparatus havlng a drum cathode slmllar to that shown ln Flg. 1, but the anode comprlses a tube wlth holes for addlng and dlscharglng electrolyte and gasses.
Flg. 4 ls a sectlonal slde vlew of another slmllar apparatus havlng a cathode drum, where the drum ls placed o~liquely for sultable sedlmentatlon of the partlcle materlal, and where the anode tube 18 surrounded by a non-conductlng sheet for reflnlng electrolysls.
In the apparatus sultable for performlng the electrolysls accordlng to the present lnventlon shown ln Flg. 1 and 2, the rotatlng cathode drum l wlth electrlcally lnsulated end plates 2 ls suspended on roll bearlngs 3. The penetratlng anode comprlses an electrlcally conductlve anode rod 4 wlth anode plates 5, preferably made of lead or some other sultable materlal, hanglng down lnto the electrolyte. The anode rod ls connected to a posltlve termlnal of a current source ~not shown). The freely movable, partlculate medlum lnslde the rotatlng cathode drum 1 mounted on a rotatable end ls glven by the reference number 7.
The partlcle materlal does not have any dlrect contact wlth the anode plate 5. The shape of the anode plates ls such that a llne formed by connectlng lower edges of the plates ls substantlally parallel wlth the surface of a bed formed of the partlculate medlum. Inslde the cathode drum 1, there ls an electrolyte 8, whlch may be dralned, optlonally together wlth produced sllt and/or waste materlal, through a dralnage openlng 10, where the electrolyte whlch ls dralned at lO ls poor ln the current catlon 4b ^ 22813-45 which 18 belng electrolysed. The electrolyte optlonally contalnlng the partlculate solld medlum, ls supplled through an openlng 9, and the drum cathode 1 ls connected at 11 to a negatlve termlnal of a current source (not shown) for example, through a slldlng connectlon. The dlrectlon of rotatlon of the cathode drum ls glven by outer arrows ln Flg. 2, and the movement of the partlculate medlum ls glven by lnner arrows ln Flg. 2.
In another posslble embodlment of the apparatus accordlng to the lnventlon, the slde walls 2 are removed, and the partlculate materlal may mlgrate towards the open ends of the cathode drum 1, and from there be taken out durlng rotatlon or shaklngJvlbratlng of the cathode drum.
A slmllar apparatus ls deplcted ln Flg. 3, where each part ls provlded wlth the same reference number as ln Flgs 1 and 2, but where the anode does not lnclude anode plates, but ls only a perforated tube and where the electrolyte solutlon stands ln dlrect contact wlth the tube 4. Thls apparatus makes lt slmple to remove produced gas through an openlng 10 by suctlon or blowlng.
Yet another slmllar apparatus for performlng the electrolysls process ls given in Fig. 4, whereln the anode tube 4 ls perforated here as well, but as mlddle anode sectlon 16-17 ls provlded wlth a non-conductlng cloth 18 and thls sectlon 14 has a separate supplylng condult 13 and an exlt condult 15 for the partlculate materlal, sllt and solutlon. For persons skllled in electrolysis lt would be obvlous that such an apparatus may be used for reflnlng of a metal or electrolysls where the so-called redox-palr are present, such as electrolysls of Cu(I) chlorlde solutlon ~cupro-solutlon) where Cu(II) chloride ls produced at the 133543~
4c ^ 22813-45 anode and may be sectioned through the cloth and out lnto the condult 15, separately from the exlt of the cathode chamber 10.
Produced gas, deplcted by bubbles ln the flgure, ls taken out through an outlet 12. Each reference number refers as well to the correspondlng elements ln the other flgures. The cathode drum shown ln Flg. 4, ls ln addltlon lncllned to produce sedlmentatlon of the partlculate medlum accordlng to partlcle slze, where large partlcles gather ln a lower part of the cathode drum and may therefrom easlly be remove.
Example for productlons of metal wlll be descrlbed herelnunder by uslng the process accordlng to the lnventlon.
Experiment 1:
- The purpose for this experiment was to determine the effect of the process according to the invention during production of metal, i.e. to determine whether metal did not deposit on the cathode walls but on the particulate material in the cathode drum only. The cathode drum (diameter = 20 cm, length = 100 cm, made of 316 L stainless steel) was filled with 4,00 kg Cu-spheres (so-called "prills") with a diameter of 3 - 5 mm, and approx. 9 1 electrolyte.
(Intervals within which the particular general trial parameters lie, are: H2SO4 - 50-200 g/l, metal concen-tration - 5-60 g/l in the inlet, temperature - 25-30C up to 70-80 C, metal cations - Cu2 , Ni2 , Zn , current density - 50-2000 A/m2, rotation of the cathode drum -1-20 rpm (corresponding to 1-20 cm/sec. periperally), weight of solid medium - 1-10 kg (corresponding to 100-1000 kg/m ).) The anode comprised in this trial 19 Lead anode plates with a mutual distance of S cm inside the cathode drum. The electrolysis device was mounted on rolls, and a variable motor rotated the drum with 17 rpm while the anode was stationary. The device was heated by help of heating cables placed around the drum (2 x 400 W) and received their energy via two sliding contacts of 220 V. A contact thermostate regulated the temperature with 5 C accuracy.
The positive end of a rectifier was connected to the anode rod which protruded from openings in the end walls of the cathode drum. The negative pole was connected to a S mm lead plate which slided against the rotating cylinder and was kept in place by a spring which gave good contact without tendencies to spark production. The system could withstand 200 A. Electrolyte was supplied 133S43~
through the one end of the cathode drum, and drained from the other end. Current was supplied when the working temperature was reached while the drum rotated continously.
Continous repacement of the particulate medium was not performed in this experiment, and the particles were allowed to grow. The experiment was done for 9~ hours at 25-28C by using 60 A. This gave a current density of 240 A/m2 at a cell voltage of 2,8 V.
The results of the experiment are given in Table l. By these operating conditions there was produced 0,3 kg copper deposited on the copper spheres in the solid medium in the cathode drum only. The drum walls per se were com-pletely free from copper deposits.
Table l.
2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 3,3 g/l 44 g/l 9,6 l/h Drained 0,l g/l 92 g/l 9,6 l/h 28C
During the experiment there was also produced hydrogen, but this was effectively removed by suction. The trial shows that metal is deposited on the solid medium only.
Experiment 2:
The same prcedure as in experiment l was used, but with increased temeperature and a supply to the cell of 32 g/l copper and a drainage from the cell of 5 g/l copper to determine whether the solid medium (the copper spheres, "prills") still were produced at increased copper concen-trations without deposits of copper on the drum walls at 50C. The results are given in Table 2. ~t the trials, the cell voltage = 2,4 V, Current density = 240 A/m , - ~7~ 133543S
Duration = 37 hours, Current efficiency = 70%. There was produced 1,8 kg metal on the solid medium alone.
5 Table 2:
2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 32,0 g/l 176 g/l 1,74 l/h Drained 5-7 g/l 260- 1,41 l/h 50 C
270 g/l Experiment 3:
The same procedure as in experiment 1 was used, except that this experiment was a copy of a true electro extraction procedure for copper, where the feed electrolyte is approx.
60 g/l Cu and the drainage is 30-40 g/l Cu at 55-60C.
The operating conditions were: Cell voltage = 2,7 V, Current density = 240 A/m2, Duration = 18 hours, Current efficiency = 55% (on account of Fe3 ). There was at the trial produced 0,70 kg copper deposited on the medium material (the copper spheres) alone. The operating con-ditions are given in table 3. The trial shows that the process according to the invention may be used under usual conditions for electro production of metal.
Table 3. 2+ 3+ Electrolyte Cu Fe H2SO4 supply Temp.
Supplied the cell 58 g/l 2 g/l 64 g/l 1,5 l/h Drained 35 g/l 2 g/l 107 g/l 1,4 l/h 55-60 C
Experiment 4:
The same procedure as in experiment 1 was used, except that the current density was increased to 800 A/m , while the temperature was kept to 55-60C with a supply of 32 g/l Cu.
(The cell current = 200 A, no iron in the supplied material.) The operating conditions are given in table 4. There was __ -8- 1335 435 produced 0,66 kg copper which was deposited on the copper medium in the drum alone. The trial was performed with cell voltage = 3,3 V, Current density 800 A/m2, duration =
4 hours, current efficiency = 70~.
Table 4. 2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 32,4 g/l 80 g/l 5,2 l/h Drained 0,1-0,4 g/l 140 g/l 4,8 l/h 55-60C
In connection with experiment 4 it is of interest to observe that the minimum content of metal ions in the drainage is 0,1-0,4 g/l. This shows that the efficiency of the process and with the device according to the present invention, is strongly improved compared to previous technique in the field.
Experiment 5:
The same procedure as in experiment 1 was used, except that the quantity of copper spheres ("prills") was increased from 4,00 kg to 8,00 kg, and the feed electrolyte from experiment 4 was doped with small quantities of antimony (Sb) and arsenic (As) to determine the selectivity of the deposition of copper against antimony and arsenic.
The trial was performed with a cell voltage of 3,0-3,6 V, current density = 800 A/m2, duration = 3 hours, temperature =
60C, feed velocity of solution = 3,3 l/h, current = 200 A.
The trial conditions an -results are given in table 5.
:, Experiment 5 shows as in experiment 4 that the drained solution contains very little metal ions, and that the selectivity for depositing copper against antimony and arsenic is very good.
133S~35 Table 5.
cu2+ H2SO4 Fe2+ Sb As Supplied the cell 27,3 g/l 171 g/l 1,4 g/l 90 mg/l 8 mg/l Time 5 min drain 28,7 " 85 " 8 "
" "20,7 " 85 " 8 "
" "9,7 " 186 " 85 " 8 "
" "3,6 " 85 " 9 "
105 " "0,75 " 85 " 9 "
10 120 " "0,13 " 1,6 " 59 " 7 "
135 " "0,13 " 203 " 34 " 4 "
In this connection it is interesting to observe that the present invention opens for possibilities for use over and above only electro production and electro refining of metal such as f.ex. inter alia purification of electrolytes.
Experiment 6.
The same procedure as in experiment 4 was used, except that the solid medium inside the cathode drum was changed from copper spheres ("prills") to small bits (5 x 5 x 10 mm) of stainless steel (316 L), the same material that the drum was made of. The trial conditions are given in table 6.
During the trial there was deposited on the steel bits a copper layer in a quantity of 0,36 kg simultaneously as there was produced copper dust in a quantity of 0,47 kg.
There was neither in this experiment deposited any copper on the walls of the cathode drum. The trial was performed with cell voltage = 3,9 V, current density = 800 A/m , duration = 5,1 hours, current efficiency = 70%.
Table 6. 2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 32,4 g/l 145 g/l 5,5 l/h Drained 0,4-0,6 g/l 210 g/l 5,1 l/h 55-60C
The trial shiws that the medium in the cathode drum needs to be present, but may be of a different material than the metal which is to be separated. This-~rcvnots all the same depositing of material on the drum walls.
Experiment 7.
The same procedure as in experiment 4 was used, except that the solid medium inside the cathode drum was replaced with ground rock (- 25 + 4 mm). This was performed to determine whether an inert medium (not electrically conducting) would prevent deposit on the walls of the cathode drum.
The trial conditions are given in table 7. At the trial there was deposited the main part (approx. 450 - 500 g Cu) on the inside of the drum walls, while there was found 0,lO g copper particles in the solid medium in the drum.
The trial was performed with cell voltage = 5 - 6 V, current density = 800 A/m2, duration = 3,6 hours.
Tabl~ 7 Electrolyte supply Temp.
Supplied the cell 32,0 g/l 145 g/l 5,5 l/h Drained 1-3 g/l 206 g/l 5,0 l/h 60-70C
The above given experiments show that if the conditions are right (e.g. metal concentration, temperature, stirring, current density etc.) in the cathode, an electrically con-ducting medium alone inside the cathode drum will effectively prevent deposition of metal on the drum walls. If the conditions by the electrolysis however favours silt/particle deposition (e.g. generally low metal concentration, low temperature, high current density and reduced stirring), the solid medium works as a mechanical grinder, and it makes no difference whether the medium is electrically conducting or not. It is preferred that the solid medium should be -- -ll- 133~5 of the same character as the metal which is removed from the electrolyte. The process and device according to the invention can accordingly advantageously be used for purification purposes during use of low current density.
Table 4. 2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 32,4 g/l 80 g/l 5,2 l/h Drained 0,1-0,4 g/l 140 g/l 4,8 l/h 55-60C
In connection with experiment 4 it is of interest to observe that the minimum content of metal ions in the drainage is 0,1-0,4 g/l. This shows that the efficiency of the process and with the device according to the present invention, is strongly improved compared to previous technique in the field.
Experiment 5:
The same procedure as in experiment 1 was used, except that the quantity of copper spheres ("prills") was increased from 4,00 kg to 8,00 kg, and the feed electrolyte from experiment 4 was doped with small quantities of antimony (Sb) and arsenic (As) to determine the selectivity of the deposition of copper against antimony and arsenic.
The trial was performed with a cell voltage of 3,0-3,6 V, current density = 800 A/m2, duration = 3 hours, temperature =
60C, feed velocity of solution = 3,3 l/h, current = 200 A.
The trial conditions an -results are given in table 5.
:, Experiment 5 shows as in experiment 4 that the drained solution contains very little metal ions, and that the selectivity for depositing copper against antimony and arsenic is very good.
133S~35 Table 5.
cu2+ H2SO4 Fe2+ Sb As Supplied the cell 27,3 g/l 171 g/l 1,4 g/l 90 mg/l 8 mg/l Time 5 min drain 28,7 " 85 " 8 "
" "20,7 " 85 " 8 "
" "9,7 " 186 " 85 " 8 "
" "3,6 " 85 " 9 "
105 " "0,75 " 85 " 9 "
10 120 " "0,13 " 1,6 " 59 " 7 "
135 " "0,13 " 203 " 34 " 4 "
In this connection it is interesting to observe that the present invention opens for possibilities for use over and above only electro production and electro refining of metal such as f.ex. inter alia purification of electrolytes.
Experiment 6.
The same procedure as in experiment 4 was used, except that the solid medium inside the cathode drum was changed from copper spheres ("prills") to small bits (5 x 5 x 10 mm) of stainless steel (316 L), the same material that the drum was made of. The trial conditions are given in table 6.
During the trial there was deposited on the steel bits a copper layer in a quantity of 0,36 kg simultaneously as there was produced copper dust in a quantity of 0,47 kg.
There was neither in this experiment deposited any copper on the walls of the cathode drum. The trial was performed with cell voltage = 3,9 V, current density = 800 A/m , duration = 5,1 hours, current efficiency = 70%.
Table 6. 2+ Electrolyte Cu H2SO4 supply Temp.
Supplied the cell 32,4 g/l 145 g/l 5,5 l/h Drained 0,4-0,6 g/l 210 g/l 5,1 l/h 55-60C
The trial shiws that the medium in the cathode drum needs to be present, but may be of a different material than the metal which is to be separated. This-~rcvnots all the same depositing of material on the drum walls.
Experiment 7.
The same procedure as in experiment 4 was used, except that the solid medium inside the cathode drum was replaced with ground rock (- 25 + 4 mm). This was performed to determine whether an inert medium (not electrically conducting) would prevent deposit on the walls of the cathode drum.
The trial conditions are given in table 7. At the trial there was deposited the main part (approx. 450 - 500 g Cu) on the inside of the drum walls, while there was found 0,lO g copper particles in the solid medium in the drum.
The trial was performed with cell voltage = 5 - 6 V, current density = 800 A/m2, duration = 3,6 hours.
Tabl~ 7 Electrolyte supply Temp.
Supplied the cell 32,0 g/l 145 g/l 5,5 l/h Drained 1-3 g/l 206 g/l 5,0 l/h 60-70C
The above given experiments show that if the conditions are right (e.g. metal concentration, temperature, stirring, current density etc.) in the cathode, an electrically con-ducting medium alone inside the cathode drum will effectively prevent deposition of metal on the drum walls. If the conditions by the electrolysis however favours silt/particle deposition (e.g. generally low metal concentration, low temperature, high current density and reduced stirring), the solid medium works as a mechanical grinder, and it makes no difference whether the medium is electrically conducting or not. It is preferred that the solid medium should be -- -ll- 133~5 of the same character as the metal which is removed from the electrolyte. The process and device according to the invention can accordingly advantageously be used for purification purposes during use of low current density.
Claims (10)
1. An electrolysis process for electrolytically producing a metal from a compound of the metal, which comprises:
applying an electric current through a cathode, a liquid electrolyte containing the compound of the metal and an anode, wherein :
the cathode is a rotatable drum rotating in operation and contains therein the electrolyte;
the anode is a rod extending between two ends of the cathode drum inside the cathode drum and comprising a plurality of electrically conductive anode plates each hanging down into the electrolyte from the anode rod, the anode being electrically insulated from the cathode drum other than through the anode plates and the electrolyte which is in contact with the cathode;
the rotatable drum further contains therein at least in an initial stage of the electrolysis an electrically conductive particulate material which is insoluble in the electrolyte under conditions of the electrolysis and is freely movable in the rotatable drum to polish an inner surface of the rotatable drum, whereby the electrolytically produced metal deposits on the electrically conductive particulate material inside the rotatable drum but not on the inner surface thereof;
the particulate insoluble material is continuously supplied into and removed from the rotatable drum cathode; and the electrolyte is continuously added into the rotatable drum cathode through one end and is continuously removed from the rotatable drum cathode through the opposite end.
applying an electric current through a cathode, a liquid electrolyte containing the compound of the metal and an anode, wherein :
the cathode is a rotatable drum rotating in operation and contains therein the electrolyte;
the anode is a rod extending between two ends of the cathode drum inside the cathode drum and comprising a plurality of electrically conductive anode plates each hanging down into the electrolyte from the anode rod, the anode being electrically insulated from the cathode drum other than through the anode plates and the electrolyte which is in contact with the cathode;
the rotatable drum further contains therein at least in an initial stage of the electrolysis an electrically conductive particulate material which is insoluble in the electrolyte under conditions of the electrolysis and is freely movable in the rotatable drum to polish an inner surface of the rotatable drum, whereby the electrolytically produced metal deposits on the electrically conductive particulate material inside the rotatable drum but not on the inner surface thereof;
the particulate insoluble material is continuously supplied into and removed from the rotatable drum cathode; and the electrolyte is continuously added into the rotatable drum cathode through one end and is continuously removed from the rotatable drum cathode through the opposite end.
2. The process according to claim 1, wherein the plurality of the electrically conductive anode plates have such a shape that a line drawn by connecting lower edges thereof is substantially parallel with the surface of a bed formed of the electrically conductive particulate material.
3. The process according to claim 1, wherein the electrically conductive particulate material is in the form of Cu prills having a diameter of from 3 to 5 mm.
4. The process according to claim 1 or 2, wherein the particulate insoluble material is of a metal or a metal alloy.
5. The process according to claim 4, wherein the particulate insoluble material is of the same metal as the metal produced by the electrolysis.
6. The process according to claim 5, wherein the metal is copper.
7. The process according to any one of claims 1 to 3, wherein a produced gas is removed during the electrolysis.
8. An apparatus adapted for performing the electrolysis process as defined in any one of claims 1 to 3, which comprises:
a cathode in the form of a drum which is rotatable about a substantially horizontal axis and is connected to a current source, the drum comprising a body and two end walls each having a central orifice which is provided with means for supporting an anode and the drum being designed for containing therein a liquid electrolyte containing a compound of the metal;
an anode which is a rod extending between the two end walls of the cathode drum inside the cathode drum and comprising a plurality of electrically conductive anode plates each hanging down into the electrolyte from the anode rod, the anode being electrically insulated from the cathode other than through the anode plates and the electrolyte which is in contact with the cathode;
means for supplying the electrolyte; and means for draining the electrolyte after use;
wherein the apparatus is designed such that the cathode is capable of containing therein an electrically conductive particulate material which is insoluble in the electrolyte under conditions of the electrolysis and is freely movable in the rotatable drum to polish an inner surface of the rotatable drum and that the metal electrolytically produced deposits onto the electrically conductive particulate material.
a cathode in the form of a drum which is rotatable about a substantially horizontal axis and is connected to a current source, the drum comprising a body and two end walls each having a central orifice which is provided with means for supporting an anode and the drum being designed for containing therein a liquid electrolyte containing a compound of the metal;
an anode which is a rod extending between the two end walls of the cathode drum inside the cathode drum and comprising a plurality of electrically conductive anode plates each hanging down into the electrolyte from the anode rod, the anode being electrically insulated from the cathode other than through the anode plates and the electrolyte which is in contact with the cathode;
means for supplying the electrolyte; and means for draining the electrolyte after use;
wherein the apparatus is designed such that the cathode is capable of containing therein an electrically conductive particulate material which is insoluble in the electrolyte under conditions of the electrolysis and is freely movable in the rotatable drum to polish an inner surface of the rotatable drum and that the metal electrolytically produced deposits onto the electrically conductive particulate material.
9. The apparatus according to claim 8, wherein the plurality of the electrically conductive anode plates have such a shape that a line drawn by connecting lower edges thereof is substantially parallel with the surface of a bed formed of the electrically conductive particulate material.
10. The apparatus according to claim 8, which further comprises means for removing a gas produced during the electrolysis.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO872243A NO872243D0 (en) | 1987-05-27 | 1987-05-27 | DRUM ELECTROLYSIS. |
| NO87.2243 | 1987-05-27 | ||
| NO87.2388 | 1987-06-05 | ||
| NO872388A NO164921C (en) | 1987-05-27 | 1987-06-05 | PROCEDURE FOR ELECTRICAL EXTRACTION OF METAL AND DEVICE FOR CARRYING OUT THE PROCEDURE. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335435C true CA1335435C (en) | 1995-05-02 |
Family
ID=26648034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000567777A Expired - Fee Related CA1335435C (en) | 1987-05-27 | 1988-05-26 | Drum electrolysis |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0319552A1 (en) |
| JP (1) | JPH01501951A (en) |
| CN (1) | CN88103116A (en) |
| AU (1) | AU598097B2 (en) |
| CA (1) | CA1335435C (en) |
| FI (1) | FI88178C (en) |
| MX (1) | MX170337B (en) |
| NO (1) | NO164921C (en) |
| WO (1) | WO1988009399A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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. |
| DE69223040T2 (en) * | 1991-02-14 | 1998-06-10 | Materials Research Pty. Ltd., Brisbane, Queensland | MINERAL PROCESSING DEVICE |
| WO1994002663A1 (en) * | 1992-07-17 | 1994-02-03 | Mallonbury Pty. Ltd. | Method and apparatus for mineral recovery |
| AU677963B2 (en) * | 1992-08-26 | 1997-05-15 | Spunboa Pty Ltd | Electrolytic oxidizer |
| CN102296325B (en) * | 2011-06-15 | 2016-05-04 | 马光甲 | Process for treating waste lead accumulator through continuous solid phase electrolysis of rotating cathode |
| CN102787330B (en) * | 2012-08-04 | 2015-01-28 | 昆明理工大学 | Electrolysis method |
| CN112877538A (en) * | 2021-01-11 | 2021-06-01 | 中南大学 | Device and method for recycling cadmium sponge by enhanced replacement of self-rotating current electric field |
| DE102021211142A1 (en) | 2021-10-04 | 2023-04-06 | Robert Bosch Gesellschaft mit beschränkter Haftung | Ball mill and process for obtaining at least one metal |
| CN115838215A (en) * | 2022-07-22 | 2023-03-24 | 苏州科技大学 | Device and method for treating refractory organic wastewater |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7008783A (en) * | 1969-06-26 | 1970-12-29 | ||
| IE39814B1 (en) * | 1973-08-03 | 1979-01-03 | Parel Sa | Electrochemical process and apparatus |
| JPS5335883A (en) * | 1976-09-14 | 1978-04-03 | Toshiba Corp | Production management data computing system |
| SE451855B (en) * | 1983-06-17 | 1987-11-02 | Svenska Utvecklings Ab | ELECTROCEDOM CELL UNIT INTENDED TO BE USED IN AN ELECTROCHEMICAL CELL WITH PORO'S FLOW ELECTRODE, ELECTROCHEMICAL CELL, PROCEDURE FOR THE PREPARATION OF THE ELECTROCHEMICAL CELL AND USED FOR USING IT |
| EP0151055B1 (en) * | 1984-01-09 | 1988-08-31 | Yves Heroguelle | Apparatus for the galvanic recovery of metals from diluted solutions |
-
1987
- 1987-06-05 NO NO872388A patent/NO164921C/en unknown
-
1988
- 1988-01-08 EP EP88900854A patent/EP0319552A1/en not_active Withdrawn
- 1988-01-08 AU AU11554/88A patent/AU598097B2/en not_active Ceased
- 1988-01-08 JP JP63501054A patent/JPH01501951A/en active Pending
- 1988-01-08 WO PCT/NO1988/000002 patent/WO1988009399A1/en active IP Right Grant
- 1988-04-04 MX MX010977A patent/MX170337B/en unknown
- 1988-05-26 CN CN198888103116A patent/CN88103116A/en active Pending
- 1988-05-26 CA CA000567777A patent/CA1335435C/en not_active Expired - Fee Related
-
1989
- 1989-01-24 FI FI890338A patent/FI88178C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FI890338A (en) | 1989-01-24 |
| EP0319552A1 (en) | 1989-06-14 |
| MX170337B (en) | 1993-08-17 |
| FI890338A0 (en) | 1989-01-24 |
| NO164921C (en) | 1990-11-28 |
| NO872388L (en) | 1988-11-28 |
| NO164921B (en) | 1990-08-20 |
| WO1988009399A1 (en) | 1988-12-01 |
| AU598097B2 (en) | 1990-06-14 |
| CN88103116A (en) | 1988-12-28 |
| FI88178C (en) | 1993-04-13 |
| FI88178B (en) | 1992-12-31 |
| JPH01501951A (en) | 1989-07-06 |
| NO872388D0 (en) | 1987-06-05 |
| AU1155488A (en) | 1988-12-21 |
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