Electrowinning is the process of electrodeposition of metal from a metal-bearing electrolyte, reducing metal ions in solution by the application of direct current electric power and is a primary technology in hydrometallurgical extraction of various metals.
A technical paper entitled, “Development of a Cathode Mandrel for Production of Nickel and Cobalt Rounds,” by Douglas J. Robinson, Dremco Inc., presented at the Alta 2000 Nickel/Cobalt-6 conference in Perth, Australia May 15-18, 2000 presents some background information:
“Nickel and cobalt, purified by electrolysis, are often used in a cut or fragmented form in subsequent electroplating cells and alloy melting furnaces. Nickel cathodes, with their Face Centered Cubic (FCC) crystal form, lend themselves to shearing into squares, while cobalt with its more brittle Body Centered Tetragonal (BCT) crystal form tends to shatter if sheared, so has been fragmented by grinding and tumbling equipment. An alternative method of obtaining sectioned products has been to produce “rounds” deposits, with an approximately 20-50 mm diameter and an approximately 2-5 mm thickness. These deposits are formed on full sized cathode blanks, where point or circular “islands” have been exposed on an otherwise insulated surface” (Robinson, supra).
An electrowinning process was developed by INCO LIMITED (Toronto) in Canada, and subsequently by FALCONBRIDGE LIMITED (Toronto) for its plant in Norway. Inco produces rounds in two sizes for nickel and a third size for cobalt. The Falconbridge product is termed a “crown,” and is nominally 12 mm in diameter. It is intentionally thicker than the round and is claimed as a superior product by its producer. These two companies enjoy a premium price for the nickel products, and so have chosen to maintain the details of their methods as proprietary, not available to competitor companies.
A recent development in electrowinning (electrodepositing) technology has been an innovation of isolating either the anodes or cathodes from the bulk electrolyte for the purpose of better controlling the acidity (measured as pH) of the electrolyte solution in direct contact with the cathode, which is where the metal is deposited.
This is accomplished by encasing the electrodes, either the anodes or the cathodes, in a box or frame equipped with a permeable membrane such that solution either flows primarily out of the cathode frame into the bulk electrolyte or from the bulk electrolyte into the anode frame.
Elevated acidity in the solution at the point of plating has detrimental effect on product metal quality and the current efficiency. The ability to maintain the solution around the cathodes at a desirable moderate pH, while allowing the solution around the anodes to become more acidic through the normal anodic chemical reactions, facilitates greater efficiencies in the overall downstream metal recovery process.
In the case of cobalt electrowinning, full sheet cathode deposits have high internal stresses and frequently separate partially from the cathode blank and curl up, thus growing faster toward the anode and penetrating the membrane. During this process, or at harvesting, the membrane is torn and the more acidic solution is no longer contained. This results in contaminating the bulk solution, thus compromising quality, and necessitates the replacement of the torn anode bags.
Producing electrowinning rounds greatly reduces the hazard of shorting through curling deposits and is thus another advantage over making full size deposits. Also, harvesting cobalt rounds is easier than harvesting the full size cathode, being generally easier to release the rounds.
There are various designs used to produce rounds. For example, U.S. Pat. No. 3,668,081 to Borner describes a thermoset epoxy ink or heat curing paint to create a reusable resist matrix on a repeatedly reusable cathode or mandrel. The epoxy ink coating lasts approximately four plating and harvesting cycles until wear and tear necessitates replacement. The removal of the epoxy ink coating utilizes a process involving hash chemicals, such as hydrofluoric acid, thus creating a waste stream.
Canadian Patent No. 1,066,657 to Parkinson describes a reusable integrated cathode unit with surface array of metal islands. This technology uses a non-conductive cathode support slab with embedded conductive metal assembly having projections at spaced intervals that penetrate the surface of the slab thereby forming an array of solid, conductive metal islands being flush with or raised above the slab separated from each other sufficiently for the electrodeposition of metal deposits.
An electrode mask for electrowinning a metal is provided. An example technique forms openings in a solid nonconductive sheet, such as vinyl, polyvinyl chloride (PVC), or other plastic and adheres the sheet as a solid to a cathode surface as a mask. The mask protects the cathode surface from electrical interaction with an electrolyte, while the openings allow controlled electrodeposition of a metal in harvestable rounds, which can be stripped from the cathode. The electrode mask is reusable, and easily removed for recycling and replacement. A matrix design engine calculates pattern and sizes for the openings in the mask to optimize electrodeposition of the metal based on multiple parameters including the metal to be deposited, ions present in an electrolyte, electrolyte concentration, pH level, voltage, electrical current density, solution temperature, electrode temperature, or plating time.
This summary section is not intended to give a full description of an electrode mask for electrowinning a metal. A detailed description with example embodiments follows.
This application describes electrode masks for electrowinning metals. Example masking films described herein provide an improvement on the conventional processes of painting or coating a liquid, non-conductive, i.e., insulating material, on the face of the cathode blank 104, which then sets or dries to define a layer of insulation on the cathode 104 that has conductive islands (openings in the insulation layer). The example masking films described herein have pre-formed holes in an insulating masking film to be applied to a cathode surface 104, thereby insulating the cathode 104 against the electrolyte solution, except for the intentional holes (the conductive islands or openings) though which the cathode makes contact with the electrolyte solution. The example electrode masking films and application techniques provide more cost-effective, more durable, and easier-to-use materials and processes than conventional methods.
In an implementation, as shown in
Referring to
Example electrode masking film materials may be obtained with adhesive already attached on one side, so that application can be, for example, a peel-and-stick operation, again with relatively inexpensive equipment. The adhesive to be used can be adjusted for the best performance in a specific operation. The adhesive does not necessarily need to be pre-applied to the film, although such is a simple method.
In various implementations, many materials can be used as the electrode masking film 100 and applied to a conductive cathode surface 104 by various means of adhesion, including thermal treatment.
Cost is often a driving force in decision making. The cost of a PVC embodiment of the electrode masking film 100 is approximately equal to the cost of the conventional epoxy ink used in the conventional process. The advantages of the electrode masking film 100 start with a simpler initial application step, in which the electrode masking film 100 can be applied with a roller machine to each side of the cathode 104, which may take only a few minutes, and the cathode 104 is then ready for edge strip installation and return to service. The conventional epoxy ink technique, on the other hand, requires screen-printing the epoxy ink onto the cathode face 104, then transporting the cathode into a curing oven without smearing the wet ink, and then curing the epoxy ink at high temperature for several minutes. The cost of the screen printing equipment alone can be approximately $500,000 USD in current values, and approximately $1,000,000 to $2,000,000 USD for an entire printing, heat-curing and material-handling equipment package for a small operation. A plotting machine capable of producing the example electrode masking films 100, on the other hand, may cost approximately $5,000 USD in current value, and an application roller machine can be obtained for less than $3,000 USD. Additionally, the needed operational working area and manpower is reduced by using an example electrode masking films 100 and associated application and removal techniques, as are the associated energy costs also reduced for an example electrowinning operation.
Eventually, masking materials wear and must be replaced. The conventional methods require dissolving or loosening the epoxy masking using harsh chemicals such as hydrofluoric acid. By comparison, example removal of the PVC or plastic film of the electrode masking film 100, when necessary for replacement, also provides advantages over previous technology, for example, the removal and replacement is simpler and creates no hazardous waste. An obsolete electrode masking film 100 can be removed with grit blasting, precise wire brushing, water blasting, or by heating and scraping. Grit blasting with non-abrasive media effectively removes the electrode masking film 100 from the cathode without detrimentally impacting the cathode surface 104. Water blasting with a simple pressure washer at 3,000 psi effectively removes the electrode masking film 100, and leftover residue adhesive can be removed with a solvent. The electrode masking film 100 can also be removed by heating with a simple hand held hot air gun, scraped, and when performed correctly, most of the adhesive is removed with the film and any residue adhesive can be removed with solvent. With these methods, and depending upon the film material used, the removed material is not a hazardous waste. In the case of poly vinyl chloride, the material can be recycled, although to date, such a recycling industry for this waste is immature and yet to be widely developed.
An example plastic electrode masking film 100 is more durable and lasts longer than conventional epoxy ink electrode coatings. The example electrode masking film 100 does not break down chemically in an electrochemical cell. The electrode masking film 100 is a robust insulating material and is usually only damaged because of handling outside the cell, not inside the cell during a plating or electrowinning operation. So, when a cathode with the electrode masking film 100 is handled properly, it can have a service life several times greater than the conventional epoxy ink.
To summarize to this point, an example electrode masking film 100 is more durable and longer lasting than conventional materials used for electrowinning processes, less expensive to use because application and removal are simple steps that produce no hazardous materials, requires less labor and plant floor space area, and the cost of the associated equipment is greatly reduced.
The electrode masking film 100 described herein provides an efficient and cost effective improvement within electrowinning and electrorefining technology. In an implementation as shown in
In an implementation, the electrode masking film 100 is similar to a vinyl film used to coat traffic signs. This material technology is very well developed and the thin plastic material is often a polyvinyl chloride (PVC)-based material. Such a film withstands continuous outside exposure in the elements for years, and there are a variety of materials to choose from. Polyvinyl chloride (PVC) is a material widely used in the electrochemical industry because of its properties of chemical resistance and stability at normal operating temperatures for electrochemical processes, which can be at least as high as 160° F. Other materials may be used for the electrode masking film 100, depending upon specific chemistry in the electrochemical cell and operating conditions, and are within the scope of the invention.
The electrode masking film 100 can be machine cut to produce a matrix pattern 300 of open spaces in many shapes and configurations, and the pattern 300 can be easily modified because an example plotting and cutting machine can be CNC (computer numerical controlled) programmed which converts a CAD (Computer Aided Design) into the machining procedure. The patterns 300 cut with such machines are easily modified via programming or changing a parameter value, thus requiring no conventional hardware or equipment such as stencils that each become obsolete with design changes.
A typical cathode for use in electrowinning is approximately one meter (about 40 inches) square, and a plotting machine capable of producing such a size may cost approximately $5,000 USD in current value, as opposed to the cost of the conventional screen printing epoxy equipment, which is approximately $1,000,000 to $2,000,000 for the entire printing, heat curing, and material handling equipment package for a small operation, as introduced above. Larger conventional production operations may invest up to five times these amounts.
The pattern 300 of holes 102 cut into the electrode masking film 100 can be of many patterns 300 of hole shapes and hole arrangements. Traditionally, round shaped holed 102 provide preferred performance because they produce even patterns of deposition, thus the metal deposits 200 grow uniformly. This is an advantage for producing smooth deposits with minimal inclusion of contaminants, whereas square shapes have been shown to produce concentrated metal deposit at the corners, which is undesirable. Any shape for the holes 102 can be made in the electrode masking film 100, however, though circular holes 102 arranged in staggered rows have proven to produce a uniform product of deposited metal 200 and also utilize the plating area most efficiently. An example plotting machine can cut many patterns 300 and many sizes and shapes of the holes 102 as desired and the holes 102 and patterns 300 can be changed with simple programming adjustment.
In an implementation, the pattern 300 consisting of a matrix of holes 102, which provides the bare plating areas, ends a small distance from the edges of a cathode blank in order to allow installation of edge strips on the sides and bottom if desired, and also at the top of the cathode blank to avoid incomplete plating patterns on the deposits at the top when there are fluctuations in the electrolyte level or the interference of floating acid mist containment materials. When such is not an operational concern, the holes 102 can extend in the pattern 300 above the solution line to provide maximum plating area. Typically, an area of the electrode masking film 100 with no holes 102 would extend above the solution line to avoid plating any irregular metal deposits above the uniform matrix pattern 300.
Application of the electrode masking film 100 can be performed manually by hand with simple tools or with a roller application machine, which may cost approximately $3,000. For example, an example machine can be obtained from Highway Handyman (Eagan, Minn.).
Stainless steel or titanium cathode blanks can withstand many cycles of application and removal of the electrode masking film 100. The plating surfaces of cathode blanks are maintained to certain standards to assure good performance as a mandrel for electrodepositing metal from solutions. The surface roughness must be within limits set by standard to strike a balance of providing sufficient roughness for the electrodeposited metal 200 to adhere throughout the plating cycle, while not dislodging under its own weight, called pre-stripping. But the cathode surface 104 must not be overly rough, so that the metal deposit 200 can release when harvesting the deposited metal 200 during stripping at the end of the plating cycle. Nicks, gouges and pitting can cause the deposited metal 200 to attach, or mechanically key, onto the cathode blank and then become stubborn or impossible to release during normal harvesting operations. So it is important that the electrode masking film 100 not alter the cathode surface 104 during application or removal.
Prior to application of the electrode masking film 100, the cathode blank is inspected for surface damage, which can be repaired at that time. The blank is cleaned and dirt, oil, and organic waste removed, then the cathode blank surface 104 is allowed to dry. If the electrode masking film 100 is not applied by hand, the in an implementation, the cathode is positioned at the roller application machine and the electrode masking film 100 is applied first to one side, then the other. The cathode is then fitted with plastic edge strips to insulate the edges from electrolyte and from electrical current so that the metal is deposited only on the flat sides of the cathode and does not wrap around the edges. The electrode masking film 100 can be manufactured such that it overlaps the cathode blank and can be installed to cover the edges, which then insulates the cathode blank from the electrolyte. In such a scenario, the edge strips serve primarily to protect the electrode masking film 100. Electroplating insulation tape is commonly applied to the cathode edges under the edge strips, and can also be utilized in this an example application, overlapping the electrode masking film 100 on either side to assist the function of sealing the cathode edges from the electrolyte. As with any electrowinning or electrorefining process, it is best to keep the cathode blank surfaces free of dirt and contamination prior to inserting into the cells.
At harvesting, the cathodes are withdrawn from the cells, washed, and the metal deposits 200 are removed manually or mechanically. If any part of the insulating matrix is damaged so as to allow electrolyte to leak onto an unintended part of the cathode surface 104 and create an errant deposit, often called a nodule in reference to the typical random round shape of the metal deposit 200, the errant nodule can be removed and a small patch applied to the damaged spot to extend the service life of the electrode masking film 100. If damage has occurred to a circle boundary of a hole 102, a round patch can be applied to reinforce the boundary of the original circular hole 102 or a patch of slightly smaller diameter applied to create a deposit area (hole 102) with a fresh edge. Either repair procedure is intended to extend the life of the electrode masking film 100 at least a few more plating cycles. Otherwise, the cathodes are taken out of service for film replacement on a regular interval based on performance at the individual electrorefining plant. The electrode masking film 100 can be a robust insulating material and is damaged primarily through handling outside the cell. The electrode masking film 100 is an effective barrier to plating metal under the edges of the of the bare areas of the cathode surfaced 104, but when this does occur, the harvesting procedure can loosen part of the electrode masking film 100 and cause subsequent plating with each cycle until the cathode is removed from service and the electrode masking film 100 replaced.
At block 402, openings are formed in a nonconductive sheet. The openings, or holes 102, can be formed when the nonconductive sheet or film is being manufactured. Alternatively, the openings or holes 102 can be cut into the nonconductive sheet or film after manufacture, e.g., by a plotting machine or cutting device. The nonconductive sheet or film may be a plastic, such as vinyl or a PVC film or sheet.
At block 406, the nonconductive sheet is adhered to a cathode for electrorefining a metal. The nonconductive sheet may be applied by hand or by an application roller machine, for example. The resulting cathode with the electrode masking film 100 applied is ready to submerge in an electrolyte and receive deposition of a metal from the electrolyte by electron exchange with the electrolyte at the holes 102 in the electrode masking film 100.
At block 502, an electrode masking film 100 is removed from a cathode.
At block 504, the electrode masking film 100 is recycled to make subsequent masking film, via plastic recycling.
The example computing device 600 is only one example of a computer, controller, or computing apparatus, and is not intended to suggest any limitation as to scope of use or functionality of the computing device 600 or its possible architectures. Neither should computing device 600 be interpreted as having any dependency or requirement relating to one or a combination of the components illustrated in the example computing device 600.
Computing device 600 includes one or more processors 604 or processing units, one or more memory 606 and/or volatile storage components, one or more input/output (I/O) devices 608, and a bus 610 that allows the various components and devices to communicate with one another. Bus 610 represents one or more of any of several types of bus structures, including a memory bus or memory controller, a peripheral bus, an accelerated graphics port, and a processor or local bus using any of a variety of bus architectures. Bus 610 can include wired and/or wireless buses.
The memory 606 can be volatile media, such as random access memory (RAM), or read-only memory (ROM), for example. The example computing device 600 may also include nonvolatile data storage media 612, such as a hard drive, internal flash memory, and so forth. Data storage component 612 can include a media drive interface 614 to receive removable media 616, such as an optical disk, flash memory drive, removable hard drive, magnetic disks, and so forth.
One or more input/output devices 608 controlled by a user interface controller 618 allow a user to enter commands and information to computing device 600, and also allow information to be presented to the user on a display and audio equipment. Examples of input devices include a keyboard, a cursor control device (e.g., a mouse), a microphone, a scanner, and so forth. Examples of output devices include a display device (e.g., a monitor or projector), speakers, a printer, a network card, and so forth.
A network interface 620 allows the example matrix design engine 602 to communicate with external hardware, such as a plotter 622. The matrix design engine 602 can determine the configuration and pattern 300 of holes 102 to be formed of cut in the electrode masking film 100. An example matrix design engine 602 can optimize the size (and sometimes shape) of the holes 102, as well as the geometry of the pattern 300, including layout, angles, and spacing of the holes relative to each other and to the pattern 300, and the overall extent of the pattern on an electrode surface 104. The matrix design engine 602 can control the total amount of bare electrode area to be exposed to an electrolyte solution, for example. The holes 102 and the pattern 300 may be varied by the matrix design engine 602 to optimize metal deposition onto a cathode. The matrix design of holes 102 and pattern 300 implemented by the matrix design engine 602 can be created and varied depending on multiple parameters, such as the particular metal(s) and associated metal ions being deposited, electrolyte concentrations, pH levels, electrical voltages, electrical current densities, solution temperatures, electrode temperatures, and plating time, for example.
The example matrix design engine 602 and various other techniques may be described herein in the general context of software or program modules. Generally, software includes routines, programs, objects, components, data structures, and so forth that perform particular tasks or implement particular abstract data types. An implementation of these modules and techniques, such as the example matrix design engine 602, may be stored on or transmitted across some form of tangible computer-readable data storage media, for example local data storage 612 or removable media 616. Computer readable media can be any available tangible medium or media that can be accessed by a computing device.
Computer storage media include volatile and non-volatile, removable and non-removable tangible media implemented in a method or technology for storage of information, such as computer readable instructions, data structures, program modules, or other data. Computer storage media include, but are not limited to, RAM, ROM, EEPROM, flash memory, and other memory technology; CD-ROM, digital versatile disks (DVD), or other optical storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, and other tangible media that can be used to store the desired information and which can be accessed by a computer.
Although only a few example embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the example embodiments without materially departing from the subject matter. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the recited function and not only structural equivalents, but also equivalent structures. It is the express intention of the applicant not to invoke 35 U.S.C. §112, paragraph 6 for any limitations of any of the claims herein, except for those in which the claim expressly uses the words ‘means for’ together with an associated function.
This patent application claims the benefit of priority to U.S. Provisional Patent Application No. 61/692,114 to Valentine, filed Aug. 22, 2012 and entitled, “Electrode Mask for Electrowinning a Metal,” which is incorporated herein by reference in its entirety.
Number | Date | Country | |
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61692114 | Aug 2012 | US |