EP0094308B1 - Procédé et appareil de préparation de métal par électrolyse, notamment de plomb - Google Patents

Procédé et appareil de préparation de métal par électrolyse, notamment de plomb Download PDF

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Publication number
EP0094308B1
EP0094308B1 EP83400915A EP83400915A EP0094308B1 EP 0094308 B1 EP0094308 B1 EP 0094308B1 EP 83400915 A EP83400915 A EP 83400915A EP 83400915 A EP83400915 A EP 83400915A EP 0094308 B1 EP0094308 B1 EP 0094308B1
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Prior art keywords
electrolyte
chloride
particles
process according
lead
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German (de)
English (en)
French (fr)
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EP0094308A3 (en
EP0094308A2 (fr
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Claude Palvadeau
Claude Scheidt
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Societe Miniere et Metallurgique de Penarroya
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Societe Miniere et Metallurgique de Penarroya
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    • 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
    • C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • 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

Definitions

  • the present invention relates to the preparation of a metal by electrolysis, and in particular the preparation of lead from metal chloride. It relates in particular to the electrolysis of very pure solutions of lead chloride.
  • French Patent No. 2,240,956 describes a process for depositing metallic lead from aqueous solutions of lead chloride. More precisely, this patent describes the electrolysis of such a solution in a diaphragm cell, in the presence of ferrous chloride which oxidizes to ferric chloride during the operation; in Example 1 of this patent, the concentration of lead in the electrolyte is reduced to a value between 25 and 11 grams per liter, in a 3M solution of ferrous chloride, with a current density of 323 Alm 2 and a Faradic yield of 70%.
  • the patent does not indicate the properties of metallic lead deposition such as its density, its adhesion to the cathodic support (lead sheet), its compact or pulverulent nature or its purity, nor the mode of extraction of lead.
  • French Patent No. 2,427,401 describes a process for recovering lead from sulphide ores. This process ensures the regeneration of the reagent, ferric chloride, at the anode of an electrolyser comprising neither a diaphragm nor a membrane.
  • Lead is deposited on a cathode formed by an assembly of rods mounted in special supports so that shocks can be applied to the rods due to their rotation or their mounting device. The lead formed is detached under the action of shocks and falls to the bottom of the tank. It is then evacuated.
  • This patent does not describe the effects of the electrolysis current in the vicinity of the electrode and neither describes the recovery of the lead fragments, nor the treatment of the latter before fusion.
  • US Patent No. 3,785,950 describes a process for recovering copper by electrolysis in which an electrolysis cell comprising separate vertical electrodes, a diaphragm, a cathode, a pump for circulating the electrolyte and a removal device metal, is implemented to recover copper from an attack of metallic copper.
  • the faradic yields obtained are most often less than 90%.
  • the anodic reaction is not described in general and it is not indicated if chlorine is released at the anode or if on the contrary this release is avoided, and in what way.
  • the invention relates to the preparation by electrolysis of a very pure metal, preferably lead.
  • the subject of the invention is the preparation by electrolysis of a metal present in the electrolyte in a non-cationic and in particular anionic form.
  • It relates to such a method which implements a continuous detachment of the metal which forms on the cathodes.
  • the electrolyte circulates parallel to the cathodes which are placed vertically with a speed such that its flow is of the laminar or slightly turbulent type, so that this current, in cooperation with the apparent weight of the particles, ensures detaching them from the cathodes and, simultaneously, renewing the electrolyte near the surfaces of the electrodes.
  • the invention relates to a process for the preparation of a metal, defined in claim 1.
  • the metal of the electrolysis is lead, it is present, in the form of chloride, in an amount of between approximately 5 and 50 grams per liter, preferably between 15 and 25 grams per liter in the electrolyte.
  • the alkali or alkaline earth metal chloride is preferably sodium chloride. Its concentration in the electrolyte is preferably between 230 and 300 grams per liter.
  • the density of the electrolysis current is between 500 and 1,500 A / M 2 , preferably between 700 and 1,000 Alm 2. It is preferable that this current density increases gradually since the start-up electrolysis.
  • the temperature of the electrolyte is advantageously between 70 and 95 ° C.
  • the cathode surface having a low density of nucleation sites is preferably formed of titanium, stainless steel or graphite.
  • the electrolyte also contains iron in the form of chloride.
  • concentration of iron is then advantageously greater than 10 grams per liter and preferably between 20 and 60 grams per liter.
  • the laminar or slightly turbulent flow of the electrolyte along the cathode surface is obtained when the electrolyte current flows near the cathodes at a speed of between 0.01 and 0.15 meters per second.
  • the removal of the particles collected at the bottom of the cell is advantageously carried out by transporting the particles out of the cell, then by densification of the particles by compression.
  • the densified particles can undergo a rolling intended to drive out the electrolyte inclusions.
  • the densified particles can also undergo fusion in the presence of soda.
  • the invention also relates to an apparatus for the preparation of a metal by electrolysis defined in claim 15.
  • the apparatus comprises bipolar electrodes.
  • the device advantageously includes a recovery hood when chlorine gas is released at the anodes.
  • the anodes are advantageously formed from a metal which cannot be attacked by the electrolyte and in deployed form.
  • the transport device can advantageously be a worm, a bucket elevator or a conveyor belt and preferably the gooseneck system described below.
  • the apparatus may also include an extruder for receiving the particles and for densifying them.
  • the method and the apparatus according to the invention have all the advantages of apparatuses in which the metal detaches automatically from the cathodes.
  • the main advantage is the almost total elimination of manipulations of the electrodes. This reduction in handling increases the useful service time of the electrolysers so that the number of electrolysis cells can be reduced, with corresponding reduction in investments.
  • the electrolyte solution contains chlorides of lead, alkali or alkaline earth metals, iron and possibly other metals, for example zinc.
  • the lead chloride solution is advantageously formed from a concentrate of lead sulphide ore which, in addition to lead, contains small amounts of zinc, copper, iron, calcium and magnesium.
  • the solution contains practically only lead and iron , the other metals being in negligible quantity.
  • the amount of lead in chloride form, present in the electrolyte is preferably greater than 5 grams per liter but it does not preferably exceed 50 grams per liter. These two values are determined according to the current densities used during the electrolysis and the circulation speeds of the electrolyte in the vicinity of the electrodes, so that the faradaic efficiency and the capacity of production are optimal.
  • the electrolyte also contains in high concentration an alkaline or alkaline-earth chloride.
  • the most advantageous is sodium chloride, for reasons of cost and availability.
  • the quantity of this chloride in solution is advantageously chosen so that the concentration of chloride ion is greater than 3 equivalent-grams (that is to say in the case of sodium chloride at approximately 200 grams per liter), preferably between 4 and 5 gram equivalent (i.e. for sodium chloride between 230 and 300 grams per liter).
  • the role of this chloride is to increase the concentration of chloride ions in the electrolyte, which makes it possible to dissolve the metals whose chlorinated complexes are soluble, and to reduce the losses by Joule effect.
  • the electrolyte also contains iron in the form of chloride.
  • the chloride ions oxidize at the anode to chlorine gas at an electrode potential of 1.2 V compared to the saturated calomel electrode (DHW).
  • the apparatus must then include a suitable collecting system.
  • the electrolyte advantageously contains iron so that, at the anode, the ferrous ion oxidizes to ferric ion at a potential close to 0.6 V / DHW. It is therefore necessary that the electrolyte contains iron in the form of ferrous iron. Not only is the chlorine no longer released at the anode, but also the energy efficiency is clearly increased.
  • the ferric chloride formed at the anode is recovered and can be used again for the treatment of lead sulphide ores and the transformation of galena into elemental sulfur and lead chloride.
  • the concentration of iron in the electrolyte, in the chloride form is preferably between 20 and 60 grams per liter, and advantageously it is of the order of 40 grams per liter. It is important that this concentration is at least equal to 20 grams per liter in the anolyte, that is to say near the anodes.
  • the nature of the electrodes used and in particular of the cathodes is important for the implementation of the invention. It is found in fact that many materials are too "active, that is to say form too many nucleation sites. As a result, lead particles begin to form at too many locations on the surface of the cathodes and cannot magnify individually. For this reason, it is essential according to the invention that the density of the nucleation sites, under the electrolysis conditions used, is sufficiently low so that the particles can reach a dimension of at least 100 micrometers without joining with the particles. adjacent. Preferably, the particles retain their individuality until they reach a dimension of at least 600 micrometers and preferably one millimeter.
  • the particles individually have a large enough surface so that, when the electrolyte moves along the surface of the cathode, it exerts a tearing force which, in combination with the force of gravity, is sufficient for detachment particles when they have a dimension of a few hundred micrometers.
  • This density of sites is important according to the invention because, if the number of sites is too large, the particles formed are small and numerous and, when they are subsequently placed in the air, they oxidize easily because they form a pyrophoric powder. On the contrary, if the density of nucleation sites is too low, the production capacity is reduced.
  • a suitable density of nucleation sites is obtained by the use of cathodes whose surface is formed of smooth titanium. Stainless steel or graphite surfaces can also be used. Of course, other materials can also be used for carrying out the process of the invention, when these have the appropriate density of nucleation sites. This density can be obtained by an activation treatment or, more often, deactivation according to techniques known to those skilled in the art.
  • the anodes can be formed from graphite. However, as it is desirable that the transport of material is favored, it is preferable that the anodes be formed from an expanded metal, for example ruthenized titanium. However, the nature of the anode is much less important for the implementation of the method of the invention than that of the cathode.
  • the linear speed of the catholyte, parallel to the cathodes be at least 0.01 meters per second and preferably between 0.01 and 0.15 meters per second.
  • the speed of circulation of the solution which may be zero, is preferably at least 0.01 meter per second; the maximum value can be moderate, for example 0.05 meters per second, given the shape of the anodes which promote the creation of turbulence.
  • the temperature of the electrolyte is advantageously between 70 and 95 ° C, preferably between 70 and 90 ° C. No heating is necessary because the normal losses by Joule effect are sufficient to maintain the temperature in the aforementioned range.
  • the implementation of the method of the invention allows the use of very high current densities. They can be between 500 and 1,500 A / M 2 . Preferably, they are between 700 and 1000 A / M 2 .
  • the electrolysis begins at a low current density, lower than the values indicated above, and gradually increases to the chosen value, included in the aforementioned range.
  • the solution contains ferrous chloride
  • iron can deposit at the same time as lead, on the cathodes, when the current density is initially very high. The metal then adheres to the entire surface of the cathodes, so that the latter no longer have a suitable density of nucleation sites.
  • the initial use of a high current density can cause the evolution of hydrogen whose bubbles tend to cling to the metal particles so that these, instead of falling to the bottom of the electrolysis cell, tend to float.
  • the period during which the current density increases progressively or in stages, up to the desired final value, is advantageously a few hours.
  • the product obtained was in the form of individual particles having a dimension of a few hundred micrometers, for example from 300 to 600 micrometers.
  • Their shape can be branched and relatively flat, but their surface is relatively small for their volume. It is this characteristic which gives the particles formed their non-pyrophoric nature.
  • the particles are formed from very pure lead.
  • metals such as zinc, copper, cadmium, magnesium, etc. are present in an amount less than 1 ppm by weight.
  • the amount of iron is less than a few ppm by weight. It is therefore lead which does not subsequently require any refining for most applications.
  • the examples which follow give the purity of the lead obtained under different conditions.
  • the lead particles which deposit at the bottom of the cell are then extracted, using a suitable mechanism, as indicated in the remainder of this specification with reference to an apparatus intended for carrying out the method according to the invention.
  • the lead particles, when they are removed, are associated with occluded electrolyte, present in an amount between 20 and 30% by weight approximately. It is therefore desirable that the material undergoes compaction or rolling. It is in particular desirable that the particles be densified by extrusion, in a piston or roller press, exerting pressures greater than about 70 MPa. Filtration of the product is undesirable since the smallest particles may partially oxidize in air.
  • the semi-finished product of lead obtained for example in the form of a strip, is stable with respect to oxidation in air. It can be used as is in some applications.
  • lead can undergo fusion in the presence of sodium hydroxide, according to a well known technique.
  • the above description relates to the electrolysis of a solution containing ferrous chloride. This feature is not essential. When the process is carried out without ferrous chloride in the electrolyte, chlorine is released at the anodes.
  • the device used must therefore include a chlorine collection system. Such systems are well known in the electrochemical industries and are therefore not described in detail.
  • the current density can then have an increased value, between 800 and 2,000 A / m 2 , preferably between 800 and 1,200 A / m 2 .
  • the pH of the electrolyte is at an equilibrium value between 1.2 and 1.7, at a temperature of 70 to 80 ° C. This pH depends on the concentration of sulfate ions and the current density. However, it may be advantageous to work at a pH of between 2 and 3 so as to avoid the proton electrolysis reactions to give hydrogen. In this case, a pH regulation system must then be provided by adding a base which is preferably chosen so as not to add foreign ions to the electrolytes.
  • the basic sodium compounds sodium hydroxide, soda ash, or even basic lead compounds, lead hydroxide, litharge, basic lead carbonate, etc.
  • the device of the present invention comprises very many anode-cathode pairs placed in a non-isopotential manner.
  • the process which has just been explained above involves the use of numerous pumps for recirculation. These numerous pumps lead to investment costs which can be significant. This is why we have sought to develop an electrolysis device which makes it possible to reduce the number of electrolyte recirculation pumps and which in general, significantly reduce the investment costs of electrolysis devices.
  • the above electrolytic cell commonly known as a “swimming pool cell” is equipped with a series of substantially parallel rows of electrolytic cells.
  • Each cell is made up of the couple formed by an anode surface and a cathode surface.
  • all the cells are mounted in parallel, in a comb (or rake), that is to say that all the anodes in the same row have the same potential, however, as all the cathodes in the same row are also at the same potential.
  • the rows of said electrolytic-pool tank are mounted in electrical series; there is therefore a potential gradient in the tank-pool.
  • the present device which can be called “tank-channel” in order to implement the invention consists of a series of rows of anodes and cathodes mounted in parallel, the anodes of each row being preferably offset parallel to themselves by a value of between 5 and 20 centimeters in the direction of the decreasing potentials in the electrolysis cell, the distance between two rows being between 0.8 and 2 meters.
  • the cathodes of different rows and located on the same plane are joined together by partitions made of insulating material so as to limit stray or leakage currents. Although this is less important, the anodes of different rows and located in the same anode channel can be joined together by partitions made of insulating material so as to limit parasitic and / or leakage currents.
  • the assembly forms a juxtaposition of channels parallel to each other and perpendicular to the rows of electrodes.
  • Pump systems similar to those described in the present application impose a circulation of the catholyte and the anolyte, while between each cathode and each anode there is the diaphragm which was mentioned during the description of the process.
  • the device can be of the monopolar or bipolar type.
  • Bipolar mounting has advantages because it reduces energy losses (by reducing ohmic drops in the electrodes and related structures), it reduces the cost of the electrodes since they have a double role, and it simplifies the mounting of sets of electrodes, while allowing better energy efficiency.
  • This advantageous assembly poses certain configuration problems at the ends of the electrodes, in particular to avoid leakage currents, as those skilled in the art know.
  • FIG. 1 is a diagram of an example of an apparatus for implementing the method according to the invention.
  • the reference 1 designates an electrolysis tank containing an anode box 2.
  • the diaphragm is schematically identified by the reference 3.
  • the catholyte circulation circuit comprises a reservoir 4 and a circulation pump 5.
  • the catholyte circulates parallel to the plane of the cathodes which are mounted in the tank 1.
  • the anolyte circuit includes a reservoir 6 and a pump 7 which circulates the anolyte.
  • Reference 8 designates a pump intended to extract part of the anolyte which has concentrated in ferric chloride and is suitable for the treatment of lead sulphide ores.
  • Reference 9 designates the feed solution which restores the catholyte to the appropriate composition in the reservoir 4.
  • the particles which detach from the cathodes fall to the bottom of the cell and are taken up by an endless screw 10 mounted on a shaft 11 driven in rotation by a motor 12.
  • the particles arriving at the end of the screw arrive at a recipe 13 and are then treated as described above.
  • the nature of the electrodes and their mounting are as described above.
  • the diaphragm and anodes also have the properties indicated above.
  • a collecting hood must be mounted above the anodes so that it collects the chlorine which is released.
  • the adjustment of the weir makes it possible to maintain a difference in level between the catholyte and the anolyte, as indicated previously.
  • the flow rates of pumps 5 and 7 are adjusted so that the speeds of the anolyte and the catholyte, along the anodes and cathodes, have the values indicated above, that is to say at least equal to 0.01 meter per second.
  • the flow through the diaphragm is almost equal to the flow of the feed solution. In this way, the ferric iron can hardly pass into the catholyte.
  • the additional feed solution flow rates pass by overflow from the catholyte reservoir 4 to the anolyte reservoir 6.
  • the cell preferably has a trapezoidal or rounded bottom so that the falling particles are guided towards the worm.
  • a worm driven by a motor has been shown, other mechanisms are suitable.
  • bucket elevators or conveyor belts can also be advantageously used.
  • the product can also pass through an extruder which makes it undergo a prior densification, up to an apparent density of 3 to 6.
  • the extruder can be provided with a die long enough for it to seal the liquid.
  • the metallic particles formed are recovered using a gooseneck operating in batch mode.
  • the bottom of the cell is given a pyramid-like shape in order to direct the lead particles towards a swan neck which rises vertically along the cell.
  • the liquid level in the swan neck is in hydrostatic equilibrium with that of the electrolysis cell, i.e.
  • the swan neck rejection point is located 2 to 20 centimeters above the level of the surface of the catholyte: lead aggregates accumulate in the lower part of the swan neck, constituting a real plug; intermittently one or more ejectors, which can be produced by nozzles, are supplied by catholyte without solid at a rate sufficient to create a suction effect at the bottom of the cell and to achieve a linear speed of flow of the liquid in the neck swan of at least 0.5 meters per second.
  • the lead is entrained and recovered after separation of the liquid in a suitable system which is hydraulically disconnected from the electrolysis cell.
  • Lead agglomerates can also be entrained by air entrainment (air-lift).
  • the ejector (s) are disposed under the swan neck at the appropriate locations known to those skilled in the art to obtain a good “suction” or “air-lift” effect.
  • a sulfurized raw material consisting of a galena concentrate, containing 75.5% lead, 0.70% zinc, 0.85% copper, 1.40% iron, is treated with a solution of ferric chloride and sodium. , 1.0% calcium and 0.6% magnesium.
  • the electrolyzer supply solution and the electrolyte have the following compositions:
  • the electrolysis is carried out in an installation of the type shown in the figure; the circulation speed of the catholyte is 0.06 meters per second and that of the anolyte is 0.01 meters per second.
  • the cathodes are made of smooth titanium.
  • the current density, in steady state, is 550 A / m 2 .
  • the distance between the electrodes is 70 millimeters.
  • the lead obtained is in the form of particles having a length of the order of 300 to 600 micrometers and does not adhere to the cathodes.
  • the faradaic efficiency observed is 95%, and the energy yield is 0.57 kWh per kilo of lead.
  • Example 1 The same installation is used and an electrolyte of the same composition as in Example 1.
  • the circulation speed of the catholyte is 0.10 meters per second and that of the anolyte of 0.02 meters per second.
  • the current density used is 850 A / m 2 and the distance between the electrodes is the same as in Example 1.
  • the lead produced is similar to that described in Example 1.
  • the energy efficiency of electrolysis is 0.74 kWh per kilo.
  • Example 2 An installation similar to that of Example 1 is used.
  • the cathodes are formed from smooth titanium and the anodes from expanded titanium covered with ruthenium oxide. The distance between them is 70 millimeters.
  • the anodes are placed in an anode box in which the anolyte does not circulate.
  • the pressure difference between the anolyte and the catholyte is 20 millimeters of water column.
  • the installation is intended to allow the recovery of chlorine.
  • the energy efficiency of electrolysis is 1 kWh per kilo of lead.
  • the lead particles form a powder with an apparent density of between 1.5 and 2.5 and contain 20 to 30% by weight of occluded electrolyte. After densification with a rolling mill, this electrolyte is extracted from the powder.
  • the following table indicates not only the composition of the electrolyte but also the purity of the products obtained, on the one hand after rolling and on the other hand after shaping an ingot.
  • Example 3 The operating conditions are identical to those of Example 3, but the electrolyte contains 10 grams per liter of sulfate. At this concentration, the electrolysis is not disturbed by the sulfate ions and the energy yield remains substantially equal to 1 kWh per kilo of lead deposited.
  • the lead particles obtained have the same purity and the same level of electrolyte occluded as in Example 3.
  • the energy efficiency reaches 1.24 kWh per kilo of lead deposited.
  • the purity of the lead particles obtained and the characteristics before densification remain the same as in the previous example.
  • Example 6 Installation of electrodes of the same type of electrical series in the same tank
  • each cell consists of an anode and a cathode.
  • the electrolysis of copper sulphate was chosen to facilitate the measurements which essentially relate to the evolution of the leakage currents and the distribution of the current density at the surface of the cathodes.
  • the copper deposits are compact and the faradaic yield of the deposits very close to unity in a current density range of 200 to 300 amperes per square meter. Under these conditions, it is possible, by cutting the deposit into strips of equal width, to determine from the weight of each, the average current density of electrolysis on each surface element and thus to know the distribution profile of the average current density at the surface of the cathodes.
  • FIG. 2 represents the experimental device used.
  • the copper sulphate solution is kept in circulation between the tank 4, heated 5 and the channel type electrolysis tank 1 by the centrifugal pump 6.
  • Each cell 2 consists of a lead anode and a steel cathode stainless, spaced 1.6 cm apart.
  • one, two or three cells 2 can be mounted in electrical series and the spacing L between each cell can vary.
  • the diagram mainly represents the electrical connections between the anodes 7 and the cathodes 8.
  • Each cell 2 is connected externally by a conductor 9. Between each cell 2 there is a leakage current I F which decreases the overall energy efficiency of the electrolyser and which disturbs the distribution of the current density on the edges of the electrodes, mainly between the anode of a cell and the cathode of the neighboring cell.
  • the following table shows the main results obtained with an electrolyte containing 40 grams per liter of copper and 165 grams per liter of sulfuric acid. All the experiments were carried out at a temperature of 40 ° C for 15 to 20 hours.
  • the leakage currents are an important relative value with respect to the intensity of the current supplied by the rectifier 3. This relative importance will be considerably attenuated on a larger scale.
  • FIG. 4 gives by way of example the average density profile obtained on the cathodes 8 for test 2.
  • the overcurrent on the edges of the cathodes is not acceptable due to the increase in the local electrode overvoltage which may cause the appearance of parasitic reactions.
  • Figures 5 and 6 show the distribution profiles of true current density for cathodes with or without offset.

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EP83400915A 1982-05-06 1983-05-05 Procédé et appareil de préparation de métal par électrolyse, notamment de plomb Expired EP0094308B1 (fr)

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AT83400915T ATE36013T1 (de) 1982-05-06 1983-05-05 Verfahren und vorrichtung zur elektrolytischen herstellung von metallen, insbesondere blei.

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FR8207940 1982-05-06
FR8207940A FR2526446B1 (fr) 1982-05-06 1982-05-06 Procede et appareil de preparation de metal par electrolyse, notamment de plomb, et demi-produit obtenu par leur mise en oeuvre

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EP0094308A2 EP0094308A2 (fr) 1983-11-16
EP0094308A3 EP0094308A3 (en) 1984-05-23
EP0094308B1 true EP0094308B1 (fr) 1988-07-27

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DE4220849C1 (no) * 1992-06-25 1993-03-18 Schott Glaswerke, 6500 Mainz, De
US5559035A (en) * 1992-08-24 1996-09-24 Umpqua Research Company Solid phase calibration standards
DE19837641C2 (de) * 1998-08-19 2000-11-02 Siemens Ag Verfahren zum Routen von Verbindungen über ein paketorientiertes Kommunikationsnetz
US20040055873A1 (en) * 2002-09-24 2004-03-25 Digital Matrix Corporation Apparatus and method for improved electroforming
JP5632340B2 (ja) * 2011-08-05 2014-11-26 Jx日鉱日石金属株式会社 水酸化インジウム及び水酸化インジウムを含む化合物の電解製造装置及び製造方法
CN102560559A (zh) * 2012-01-04 2012-07-11 金川集团有限公司 一种生产电解镍粉方法
TWI539032B (zh) * 2013-08-01 2016-06-21 Chang Chun Petrochemical Co Electrolytic copper foil, cleaning fluid composition and cleaning copper foil method

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Also Published As

Publication number Publication date
AU1427283A (en) 1983-11-10
DK201183D0 (da) 1983-05-05
NO165033C (no) 1990-12-12
NO831606L (no) 1983-11-07
EP0094308A3 (en) 1984-05-23
JPS5931879A (ja) 1984-02-21
US4507182A (en) 1985-03-26
ZA833237B (en) 1984-10-31
PL241834A1 (en) 1984-06-18
FR2526446A1 (fr) 1983-11-10
CA1234070A (fr) 1988-03-15
AU572455B2 (en) 1988-05-12
FI831530A0 (fi) 1983-05-04
GR78859B (no) 1984-10-02
BR8302379A (pt) 1984-01-10
PT76645B (fr) 1986-02-26
ES522128A0 (es) 1984-02-01
MX158327A (es) 1989-01-25
FR2526446B1 (fr) 1986-02-21
FI831530L (fi) 1983-11-07
EP0094308A2 (fr) 1983-11-16
ATE36013T1 (de) 1988-08-15
ES8402626A1 (es) 1984-02-01
NO165033B (no) 1990-09-03
FI74306B (fi) 1987-09-30
DK201183A (da) 1983-11-07
PT76645A (fr) 1983-06-01
FI74306C (fi) 1988-01-11
DE3377507D1 (en) 1988-09-01
US4601805A (en) 1986-07-22

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