Equipment for the recovery of base metals from grid metals

Abstract

A solution related to recovering both elemental lead and lead alloys (e.g., antimony lead) from recycled LAB grid metal is disclosed. The solution may include, in part, one or more of the following: a rotating drum for rotating and hammering a mixture including lead paste, lead alloy, and solution, the rotary hammering being performed in a manner sufficient that the lead paste is no longer physically adhered to the lead alloy; a container for receiving the mixture from the drum and vibrating the mixture sufficiently to cause mass transfer within the mixture and facilitate separation of the lead alloy from the lead paste and solution; and / or a press for pressing the lead alloy into a pressed form.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Utility Patent Application No. 17 / 975,412, entitled "APPARATUS FOR RECOVERY OF BASE METALS FROM GRID METALLICS" (Attorney Docket No. AGR2221US1U), filed October 27, 2022, the entire contents of which are incorporated herein by reference. [Background technology]

[0002] Lead-acid battery (LAB) electrodes typically include a metal frame ("grid") coated with a special lead-based paste ("grid paste" or simply "paste"); the former is composed of a relatively rigid, conductive lead alloy (e.g., lead antimony), while the latter typically includes lead oxide and lead sulfate coated onto the exposed surface of the lead alloy grid. Additionally, one or two thin "cloths" may be installed over the grid-grid-paste combination to promote and maintain uniform weight distribution. This assembly, with or without the cloth, may be referred to herein as the "grid metal," "grid metal component," or simply the "metal" of the LAB.

[0003] When lead alloys and lead pastes are recovered and deoxidized together during recycling (which is not uncommon in conventional LAB recycling via smelting ("high-temperature reduction"), where lead paste and lead alloys are melted and blended together), the presence of alloying materials mixed therein results in the resulting output being lead with metallic impurities (up to 2%). Because of this impurity, such output lead requires extensive additional refining and alloying to recover pure elemental lead and recreate a clean alloy to replace the lead alloys essentially lost in the smelting. Recovering elemental lead and clean lead alloys in this manner is therefore both time-consuming and energy-intensive. Similarly, grid metals also pose challenges when recycling LAB using electrolytic processes (instead of smelting), as the presence of lead alloys in battery pastes can also result in impure lead output through electrolytic inefficiencies and / or the continued presence of alloying materials in the output lead.

[0004] Therefore, when recycling LAB, it may be desirable to recover lead alloys separately from the lead oxide component of the grid metal prior to deoxidation (smelting, electrolysis, or other treatment). Disclosed herein, therefore, are improved methods and flexible means for enabling the separate, yet efficient, recovery of both lead oxide (for conversion to pure elemental lead) and lead alloys (such as lead antimony) from the grid metal of recycled LAB. Summary of the Invention

[0005] Disclosed herein are systems, methods, processes, and / or chemical compositions for the recovery of lead oxide from recycled LAB grid metal and the separate and efficient recovery of its lead alloy. More specifically, various embodiments disclosed herein effectively separate lead paste and other lead compounds from the grid metal, with the resulting "cleaned" grid metal containing only lead alloy grids that may be immediately recycled or remelted and recast as new lead alloy grids for use in the subsequent manufacture of new lead-acid batteries. Some and various embodiments disclosed herein feature new processes, innovative electrolytic cell designs, and / or novel utilization of auxiliary chemistries necessary for the successful subsequent electrolytic processing of lead oxide from grid metal (not including the lead alloy from the grid), thereby converting such lead oxide to elemental lead while also enabling the recovery of the lead alloy for reuse.

[0006] Accordingly, various embodiments disclosed herein are directed to methods and / or systems for separating lead paste adhering to a lead alloy, which include mixing lead paste and a lead alloy with a solution to form a mixture, agitating the mixture in a manner sufficient that the lead paste is no longer physically adhered to the lead alloy, and removing the lead alloy from the mixture.

[0007] For some such embodiments, the agitating may include rotary hammering of the mixture, the rotary hammering may be achieved at least in part through the use of a rotating drum, the rotating drum may include internal baffles that at least in part contribute to the rotary hammering, the rotational speed of the rotating drum may be maintained within a range that is substantially optimal for achieving rotary hammering of the mixture, and / or the range may be a rotational speed at which portions of the mass within the drum are lifted above a central axis of the drum and then dropped below the central axis, the mixture may further include a cloth adhering to the lead paste, and agitation may cause the cloth to no longer adhere to the lead paste or lead alloy, the agitating may include vibrating a container containing the mixture, the vibration being sufficient to cause mass transfer within the mixture, the container may include a sieve through which the solution and lead paste can pass but not the lead alloy, and vibrating the container may at least in part facilitate passage of the solution and lead paste through the sieve. Certain embodiments may also include pressing the lead alloy into a pressed form. For selected embodiments, the solution may include at least one auxiliary chemical that at least partially reduces the adhesion of the lead paste to the lead alloy.

[0008] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter, nor is it an admission that any of the information provided herein is prior art to the embodiments described herein.

[0009] The foregoing summary and the following detailed description of exemplary embodiments will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the embodiments, there are shown in the drawings exemplary configurations of the embodiments; however, the embodiments are not limited to the specific methods and instrumentalities disclosed. The drawings are as follows: [Brief explanation of the drawings]

[0010] [Figure 1A] FIG. 1 is a modified block diagram illustrating the major components of an exemplary end-to-end electrochemical system for recovering near-pure lead from LAB, and illustrating the directional flow of materials between its various subsystems, representing various embodiments disclosed herein. [Figure 1B] FIG. 1B is a process flow diagram illustrating an exemplary approach for LAB recycling using the system of FIG. 1A, representing various embodiments disclosed herein. [Figure 1C] FIG. 1C is a modified process flow diagram of the process shown in FIG. 1B to further illustrate in greater detail the separate processing of other recyclables and dross processing, representing various embodiments disclosed herein. [Figure 2A] FIG. 1 provides a perspective view of an electrolyzer cell 100, representative of various embodiments disclosed herein. [Figure 2B] 2B provides a perspective view of the anode and interior of the electrolyzer cell of FIG. 2A, representing various embodiments disclosed herein. [Figure 3A] 2C and 2D provide a cutaway side view of the electrolyzer cell of FIGS. 2A and 2B in an initial, ready-to-use configuration for conducting electrolysis, representing various embodiments disclosed herein. [Figure 3B] 2C and 2D provide a cutaway side view of the electrolyzer cell of FIGS. 2A and 2B after being filled with electrolyte for electrolysis, representing various embodiments disclosed herein. [Figure 3C] 2C and 2D provide cutaway side views of the electrolyzer cell of FIGS. 2A and 2B after electrolysis has been performed and liquid components have been drained from the electrolysis compartment, representing various embodiments disclosed herein. [Figure 3D] 2C and 2D provide cutaway side views of the electrolyzer cell of FIGS. 2A and 2B after the final product of electrolysis has been scraped from the horizontal cathode surface and removed from the electrolysis compartment, representing various embodiments disclosed herein. [Figure 4A]FIG. 1 provides a perspective view of a vertical stack of electrolyzer cells, representing various embodiments disclosed herein. [Figure 4B] FIG. 1 provides a perspective view of a lateral line comprising multiple stacks of electrolyzer cells, representing various embodiments disclosed herein. [Figure 4C] FIG. 1 provides a perspective view of a parallel arrangement of multiple laterals, each comprising multiple stacks of electrolyzer cells, representing various embodiments disclosed herein. [Figure 5A] Annotated chemical diagrams of the molecular structures of lead monoxide (PbO), lead dioxide (PbO2), and lead hydroxide (Pb(OH)2) (collectively known as "lead oxide compounds" or "lead oxides"). [Figure 5B] Annotated chemical diagram of the molecular structure for lead sulfate (PbSO4), shown for clarity with and without bond charge (i.e., with the lead (Pb) atom juxtaposed with two oxygen atoms that have single bonds with the sulfur atom). [Figure 6A] FIG. 1B is a partially modified block diagram illustrating the major components of an exemplary cleaning subsystem, based in part on the system shown in FIG. 1A, for recovering lead oxide from non-lead components (NLC) during lead-acid battery (LAB) recycling, representing various embodiments disclosed herein. [Figure 6B] FIG. 1B is a partially modified process flow diagram illustrating an exemplary washing process, based in part on the approach shown in FIGS. 1B and 1C, for recovering lead oxide from non-lead components (NLC) during lead-acid battery (LAB) recycling, representing various embodiments disclosed herein. [Figure 7A] FIG. 1 is a modified process flow diagram illustrating an exemplary process for separating lead paste adhering to crushed lead alloy components to facilitate recovery of elemental lead from the former and to clean the lead alloy from the latter in a manner representative of various embodiments disclosed herein. [Figure 7B] FIG. 2 is a modified block diagram illustrating the major components of an exemplary paste separation unit (PSU) representative of various embodiments disclosed herein. [Figure 7C] FIG. 1 is a simplified block diagram showing a side cutaway view of the major components of an exemplary alloy separation unit (ASU), representing various embodiments disclosed herein. [Figure 8] FIG. 1 is a block diagram of an exemplary computing environment that can be used in connection with any of the various implementations and aspects disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0011] Elemental metals such as gold, silver, copper, zinc, and lead can be recovered from materials containing these metals by various electrolytic processes (e.g., electrolysis). For example, with regard to the recycling of lead-acid batteries (LAB), the lead paste obtained therefrom (typically containing a portion of pure lead as well as lead monoxide, lead dioxide, and lead sulfate) can be dissolved with or mixed in an electrolyte, and the resulting solution or mixture can then undergo electrolytic recovery of pure elemental lead (Pb) at the cathode of an electrolytic device. Similarly, lead dross obtained from such electrolytic processes as well as conventional smelting processes (typically containing pure lead as well as a portion of lead monoxide) can be further processed to mechanically remove the pure lead component, and the remainder can be dissolved with or mixed in an electrolyte, and the resulting solution or mixture can then undergo electrolytic recovery of pure elemental lead (Pb) at the cathode of an electrolytic device.

[0012] However, while conceptually simple and easily implemented on a small scale, economical recovery of lead from battery pastes and the resulting lead dross via an industrial-scale electrolytic process undertaken with sufficient yield and purity and in an environmentally friendly manner as an alternative to existing approaches requiring high-temperature smelting has heretofore been impractical, if not entirely feasible. The electrode materials for lead recovery are relatively expensive, and the operating conditions at the electrode tend to promote the formation of undesirable by-products. In existing electrolytic approaches, insoluble lead dioxide frequently forms at the anode, limiting current flow and gradually reducing operating efficiency. Similarly, lead produced at the cathode using an acidic electrolyte will deposit as a film on the cathode surface, and this lead can be difficult to remove from the cathode. When the current, i.e., the power supply driving the electrolysis, is interrupted, this deposited lead also redissolves in the electrolyte. Other drawbacks exist.

[0013] Disclosed herein are systems, processes, and chemical compositions for recovering elemental metals from impure sources on an industrial scale without smelting, particularly the recovery of elemental lead resulting from recycled LAB (including, but not limited to, dross-produced electrolytic processing, conventional smelting, or any other methodology that produces lead-containing dross). While various embodiments disclosed herein may be described as particularly related to the recovery of elemental lead from lead oxide, lead paste, and dross resulting from recycled LAB, such embodiments may be equally applicable to the recovery of other metals. Thus, nothing herein is intended to limit such embodiments to lead, lead paste, or lead dross, nor is it intended to limit such embodiments to LAB recycling; on the contrary, the disclosure made herein should be read as broadly as possible to apply to a variety of different metals extracted from various impurity forms and / or recovered from a variety of potentially different sources.

[0014] An understanding of various concepts contributes to a broader and more complete understanding of the various embodiments disclosed herein, and those skilled in the art will readily appreciate the impact of these various concepts on the breadth and depth of the various embodiments disclosed herein. Certain terms used herein may also be used interchangeably with other terms used herein, and such terms should be given the broadest possible interpretation unless otherwise specified. For example, as used herein, the terms electrolysis, electrowinning, and electrorefining should be treated as indistinguishable terms, such that when one term is used, the other term is also implied; thus, any use of the term electrolysis should be understood to include electrowinning and electrorefining unless explicitly distinguished. In contrast, the term "electrolytic process" is expressly intended to include and encompass electrolysis, electrowinning, and electrorefining.

[0015] Furthermore, as will be readily understood and appreciated by those skilled in the art, substances that may typically be represented by their chemical composition using subscript numbers, such as gaseous oxygen (O), water (H), etc., may conversely be represented herein in common standard numbers (i.e., O for gaseous oxygen, H for water, etc.) instead of subscript numbers, and are the same and equivalent as when subscript numbers are utilized, and no distinction should be made anywhere herein between the use of common standard numbers and the use of subscript numbers.

[0016] Electrolysis Process As is well known and readily understood by those skilled in the art, electrolysis is a technique that uses direct current (DC) to drive otherwise non-spontaneous chemical reactions. Using an electrolytic cell, electrolysis can be used to separate elements from one another. More specifically, in an electrolysis process, an electric current, specifically a direct current (DC), is passed through an electrolyte, causing chemical reactions at electrodes and decomposition of materials in the electrolyte.

[0017] The main components required to achieve electrolysis are an electrolyte, electrodes, and an external power source. An electrolyte is a chemical that contains free and mobile ions and is capable of conducting an electric current. An electrolyte may be an ion-conducting polymer, a solution, or an ionic liquid compound. For example, a liquid electrolyte may be created by "rescue," i.e., by attracting or associating ions of a solute with a solvent (such as water) to create mobile clusters of ions and solvent molecules.

[0018] To achieve electrolysis, electrodes (suitably connected to a power source) are immersed in an electrolyte but separated from each other by a sufficient distance so that current flows between the electrodes through the electrolyte, completing an electric circuit. In this configuration, a direct current supplied by the power source attracts ions toward each oppositely charged electrode, driving a non-spontaneous reaction.

[0019] Each electrode attracts ions of the opposite charge; positively charged ions ("cations") migrate toward the negatively charged cathode, where they donate electrons, and negatively charged ions ("anions") migrate toward the positively charged anode, where they extract electrons. In effect, electrons are introduced at the cathode (as reactants) and removed at the anode (as the desired end product). The loss of electrons is called oxidation, and the gain of electrons is called reduction.

[0020] The cathode may be made of the same material as the anode, but is typically made of a more reactive material instead, since wear on the anode is generally greater than wear on the cathode due to oxidation that occurs at the anode. The anode may be made of the same material as the cathode, but because wear on the anode during electrolysis is generally greater than wear on the cathode due to oxidation that occurs at the anode, the anode is often made of a less reactive material instead.

[0021] When neutral atoms or molecules gain or lose electrons (such as those that may be on the surface of an electrode), they become ions, can dissolve in the electrolyte, and can react with other ions. Conversely, when ions gain or lose electrons to become neutral, they can form compounds that separate from the electrolyte. For example, positive metal ions can deposit on the cathode in a layer. Furthermore, when ions gain or lose electrons without becoming neutral, their electronic charge is still changed in the process.

[0022] The key process of electrolysis is the exchange of atoms and ions via the addition or removal of electrons resulting from an applied direct current to produce a desired end product (or possibly multiple end products). The desired end product of electrolysis is often in a different physical state than the electrolyte and can be removed by one of several different physical processes, such as by collecting the gaseous end product from above the electrodes, by electrodepositing the dissolved end product out of the electrolyte, or by removing (e.g., scraping) the solid end product that has accumulated at one of the electrodes.

[0023] The decomposition potential of an electrolyte is the voltage required for electrolysis to occur, but the amount of end product resulting from electrolysis is proportional to the applied current, and under Faraday's law of electrolysis, when two or more electrolytic cells are connected in series to the same power source, the end products produced in the cells are proportional to their equivalent weights.

[0024] solid electrolyte In "solid-state electrolysis," a solid metal compound or mixture of metal compounds (the "active material") can be reduced to a pure metal end product via electrolysis by placing the active material in direct contact with the cathode of an electrolytic cell. However, because various active materials are not natural adhesives, placing (e.g., "sticking") the active material onto the cathode surface can be problematic.

[0025] Typically, active materials are applied directly to the cathode by removing the cathode from the electrolyte in the electrolysis cell and spreading a mixture of the active material and electrolyte on the cathode surface. After the mixture is dried on the cathode, the cathode is then suspended again in the electrolyte of the electrolysis cell. However, in industrial-scale operations, applying active materials to the cathode surface is time-consuming and expensive, due in part to the electrode size required for such application. Furthermore, during electrolysis, the active material dried and pasted on the cathode may absorb moisture from the electrolyte in the electrolysis cell, causing the applied material to break away or slide off the cathode, which also results in water-type electrolysis of this absorbed moisture, which together essentially replaces and / or eliminates the desired electrolysis reaction of the active material. In addition, any small amount of end-product that accumulates and adheres to the cathode itself can be inevitable, and removing this end-product from the cathode can be time-consuming, inefficient, and expensive.

[0026] Due to these inherent drawbacks, solid state electrolysis has not been utilized to commercially process active materials on an industrial scale, with such industries instead opting for more conventional approaches to purify the active materials that go into the desired end product, such as smelting. However, as is well known and widely understood by those skilled in the art, smelting has its own drawbacks, and therefore there remains a need for alternative refining processes and machinery to do the same on an industrial scale.

[0027] Lead-acid battery recycling Lead-acid batteries (LAB) are widely used today and, unlike other battery types, are almost completely recyclable, making them the single most recycled product today. Recycling lead is economically important as LAB production continues to increase year-over-year worldwide, but the depletion of lead-rich deposits makes new lead production increasingly difficult. However, almost all current lead recycling from LAB on an industrial scale is based on smelting, a thermometallurgical process in which lead, lead oxides (e.g., PbO and PbO), and other lead compounds are heated to approximately 1600°F to 2200°F (900°C to 1200°C) and then mixed with various reducing agents to remove oxygen, sulfates, and other non-lead materials. Unfortunately, lead smelting is highly polluting due to the production of significant airborne wastes (e.g., lead dust, arsenic, carbon dioxide, and sulfur dioxide), solid wastes (e.g., slag containing toxic compounds of lead and other heavy metals), and liquid wastes (e.g., sulfuric acid, arsenic, and other heavy metals and their oxides). In fact, pollution resulting from smelting is so high that many smelters in the United States and other Western countries have been forced to close to protect the environment. And while migration and the expansion of smelting in countries with less stringent regulations has led to large-scale pollution and high levels of human lead exposure in these countries, similar reduction measures are expected in these countries as time passes and new technologies become available.

[0028] While numerous approaches for recycling lead from LAB are known in the art, they all suffer from one or more drawbacks that make them impractical. Thus, there remains a need for improved devices and methods for scalable, non-smelting recycling of LAB that minimize environmental impact and achieve maximum lead recovery without excessive cost. And while several efforts have been made to move away from smelting operations and use more environmentally friendly solutions, to date, all efforts have fallen short for a variety of reasons, ranging from various pollution issues to low yields and low profitability to LAB-type solutions that cannot be effectively or efficiently scaled up.

[0029] Electrolysis Process As briefly mentioned herein above, elemental metals such as gold, silver, copper, zinc, and lead can be recovered from materials containing these metals by various electrolytic processes (e.g., electrolysis). For example, with respect to the recycling of lead-acid batteries (LAB), the lead paste obtained therefrom, which typically contains pure lead and portions of lead monoxide, lead dioxide, and lead sulfate, can be dissolved with or mixed in an electrolyte, and the resulting solution or mixture then undergoes electrolytic recovery of pure elemental lead (Pb) at the cathode of an electrolytic device.

[0030] However, while conceptually simple and easily implemented on a small scale, economical recovery of lead from battery pastes via an industrial-scale electrolytic process with sufficient yield and purity (as an alternative to existing approaches requiring high-temperature smelting) and undertaken in an environmentally friendly manner has heretofore been impractical, if not entirely feasible. Electrode materials for lead recovery are relatively expensive, and the operating conditions at the electrode tend to promote the formation of undesirable by-products. In existing electrolytic approaches, insoluble lead dioxide frequently forms at the anode, limiting current flow and gradually reducing operating efficiency. Similarly, lead produced at the cathode using an acidic electrolyte deposits as a film on the cathode surface, and this lead can be difficult to remove from the cathode. When the current (i.e., the power supply driving the electrolysis) is interrupted, this deposited lead also redissolves in the electrolyte. Other drawbacks exist.

[0031] Therefore, there is a need in the art and industry for scalable, cost-effective, and environmentally friendly solutions that enable the extraction and / or recovery of pure elemental metals from impure sources, such as, for example, the recovery of near-pure lead (Pb) during LAB recycling.

[0032] As used herein (both heretofore and hereafter), the term "near pure" shall mean a purity comparable to within 90% of the average purity obtainable by conventional smelting processes. Similarly, the term "pure" shall mean a purity equal to or exceeding the typical purity level obtainable by conventional smelting processes, and the term "perfect purity" shall mean a purity of 99.000% composed of elemental metal, regardless of natural surface oxidation or hydroxide. Thus, for all embodiments disclosed herein for obtaining "near pure" metal, such disclosure should be considered to also disclose alternative embodiments for obtaining "pure" and "perfectly pure" metal as well. Also, as used herein, the term "recovery" and other equivalent terms (e.g., refining, derivation, etc.) shall refer to obtaining a higher purity metal (e.g., elemental lead) from a less pure form of the metal (e.g., lead oxide) via electrolysis or other electrolytic processes.

[0033] FIG. 1A is a modified block diagram 10 illustrating the major components of an exemplary end-to-end electrochemical system for recovering near-pure lead from LAB, and illustrating the directional flow of materials between its various subsystems, representing various embodiments disclosed herein.

[0034] In FIG. 1A , LAB designated for recycling can be provided by LAB source 12 (shown using dotted lines to indicate inputs or outputs for the system) to LAB shredder 14, where the LAB can be physically reduced and separated into five major components: battery acid (if present), plastic, grid metal, separator, and lead paste. The battery acid, typically sulfuric acid (H2SO4), can then be output to acid neutralizer 16 for further processing, although this operation may not be necessary (and thus optional) when the LAB provided by LAB source 12 has already removed the battery acid or when no acid is otherwise present. The LAB shredder can also include plastic washer 40 to remove lead residue (typically lead monoxide) adhering to the surface of the plastic before outputting the lead-free (or nearly lead-free) plastic to plastic recycler 18. While not shown, for certain embodiments, a similar washing function can also be applied to the grid metal to recover any lead residue adhering to the grid metal. Furthermore, the separators broken down by the LAB crusher 14 are transported to the separator purifier 22 and then transported to the lead paste desulfurization device 24 together with the lead paste derived from the LABs crushed by the LAB crusher 14 (either directly and / or from the plastic washer 40) and the remaining non-lead separator components output to the separator recovery machine 46.

[0035] Because cleaning the grid metal cannot (and typically does not) completely recover the oxidized lead from the lead paste adhering to the grid metal broken down by the LAB shredder 14, the grid metal may be separated from other shredded LAB components and sent to a metal recoverer 20 to recycle its lead content, which supports the recovery of pure lead (Pb) from the lead paste adhering to the grids and ultimately transports the recovered pure lead to a melter 32 (described below) while appropriately outputting (e.g., disposing of or further recycling) the lead alloy of the grids for reuse, for example, in the manufacture of new grids for new LABs. The metal recoverer 20 and grid metal recycling are disclosed in more detail later herein.

[0036] Lead received by the lead paste desulfurization device 24 directly from LAB shredding in the LAB crusher 14, from its plastic washer 40, and / or from the separator purifier 22 typically contains elemental lead (Pb), lead monoxide (PbO), and lead dioxide (PbO), as well as lead sulfate (PbSO). The lead paste desulfurization device 24 processes the lead paste to remove sulfur from the lead sulfate (PbSO), which is a highly harmful environmental pollutant. This desulfurization can be accomplished by introducing sodium hydroxide (NaOH) into the lead paste to chemically convert the lead sulfate (PbSO) to lead hydroxide (Pb(OH)) and the sodium hydroxide (NaOH) to sodium sulfate (NaSO), which is then removed from the paste by the lead paste desulfurization device 24 using any of a variety of means known and understood by those skilled in the art. Additionally, barium sulfate (BaSO) may also be added to the lead paste as an additive before or during the desulfurization process; the barium sulfate does not react with sodium hydroxide (NaOH) during desulfurization and is intentionally retained in the resulting (and otherwise "desulfurized") lead paste in anticipation of later removal by a subsequent subsystem. Thus, the desulfurization achieved by lead paste desulfurization apparatus 24 intentionally removes only sulfur from lead sulfate (PbSO). Nevertheless, the desulfurized lead paste (which in this case contains only metallic lead in the form of elemental lead (Pb), lead monoxide (PbO), lead dioxide (PbO), and lead hydroxide (Pb(OH))) may then be passed through slurry mixer 26, where the desulfurized lead paste is combined with electrolyte 42 and auxiliary chemicals 44 (discussed in more detail later herein) to form a lead slurry solution or mixture.

[0037] In particular, for certain alternative embodiments of system 10, plastic, grid metal, separators, and lead paste may be provided directly and / or separately to system 10 in already crushed form by one or more input sources (not shown) instead of LAB source 12, in which case such input may bypass LAB crusher 14 and proceed accordingly to other appropriate subsystem(s). Similarly, for certain other alternative embodiments, lead paste may instead be provided directly to the system, i.e., to lead paste desulfurizer 24 if not already desulfurized, or to slurry mixer 26 if already desulfurized (specifically, for lead sulfate (PbSO), but not for barium sulfate (BaSO) as described above).

[0038] In the slurry mixer 26, and for some such embodiments disclosed herein, sodium hydroxide (NaOH) may also be used as the electrolyte for subsequent electrolytic treatment (e.g., electrolysis) of the lead paste, in which case the resulting lead slurry would be a mixture of the desulfurized lead paste and the electrolyte (not a solution thereof in the chemical sense). The lead slurry is then transferred from the slurry mixer 26 to the electrolytic cell 28 for electrolytic treatment (described in more detail later herein). The electrolytic cell 28 operates to produce elemental lead (Pb) substantially deoxidized from the lead monoxide (PbO), lead dioxide (PbO), and lead hydroxide (Pb(OH)) found in the lead slurry.

[0039] For certain other alternative embodiments of system 10, instead of desulfurizing the impurity metal materials before combining them with the electrolyte to form a slurry, the sulfur-containing impurity metal materials can be combined with the electrolyte to form a sulfur-containing slurry, and the electrolytic cell itself can be utilized to desulfurize the impurity metal materials before or during said electrolysis. For example, this additional functionality for the electrolytic cell can be achieved through consumption of the stoichiometric corrosion products contained in the electrolyte, resulting in the in-situ production of sodium sulfate that can be separated from the resulting deoxidized lead in subsequent processing.

[0040] Nevertheless, the resulting deoxidized lead may then be transferred to converter 30 for conversion into solid bricks with minimal amounts of electrolyte and / or auxiliary chemicals. In the case of a lead slurry mixture (but not a solution), most of the electrolyte and / or auxiliary chemicals may be extracted by electrolytic cell 28 before being transferred to converter 30, and / or the converter may include physically pressing the deoxidized lead into solid bricks, which pressing is also effective in removing most of the residual electrolyte and / or auxiliary chemicals. In contrast, in the case of a lead slurry solution, converter 30 may instead precipitate the deoxidized lead, thereby separating it from the electrolyte and auxiliary chemicals before subsequently pressing it into bricks.

[0041] The lead bricks, which may still have some minimal amount of electrolytes, auxiliary chemicals, and other impurities, including, but not limited to, barium sulfate (BaSO), lead oxides (lead monoxide, lead dioxide, and / or lead hydroxide), and any new natural oxidation occurring on the surface of the bricks, are then sent to the melter / caster 32 for melting, removal of dross, and casting as output ingots of near-pure lead 48. This melting and casting may also include as an input any pure lead recovered by the grid metal recovery machine 20, previously identified and described in more detail later herein. Alternatively, the dross may be passed to a mechanical separator 34 to separate elemental lead (Pb) and then returned to the melter / caster 32, where the lead monoxide (PbO), together with other impurities, may form lead dross and be returned to the slurry mixer 26 for inclusion in the next mixture of lead slurry for further processing (disclosed in more detail later herein). Separately, for selected embodiments, barium sulfate (BaSO), electrolyte, and auxiliary chemicals (and their residues) may be recovered and / or recycled at various points in the system (not shown).

[0042] Typically, the dross is physically skimmed onto the edge of the melting container (sometimes called a "kettle" or "pot") and manually or mechanically shoveled (or "spooned") into a separate container. Historically, dross was manually removed from large kettles by two people: one using a pusher to push the dross across the surface of the molten metal bath, and another equipped with a perforated spoon operated to scoop up the dross, allowing the molten lead to drain through perforations in the spoon and back into the kettle, before discharging the dross into a separate dross container. Many processes essentially replicate this historical methodology using manual, mechanical, or combined manual / mechanical means that are well known and readily understood by those skilled in the art, as do other mechanical dross removal methods such as "vacuum dross" and other non-traditional approaches.

[0043] Figure 1B is a process flow diagram 60 illustrating an exemplary approach for LAB recycling using the system of Figure 1A, representing various embodiments disclosed herein. In Figure 1B, LAB received for recycling can be crushed at 62 to produce lead paste and other recyclables, the latter of which can be separately processed at 64, generally as previously described herein with respect to Figure 1A. Any additional lead recovered from this separate processing can be returned and combined at 62 with the lead paste resulting directly from crushing.

[0044] The lead paste derived at 62 (and 64, if present) can then be desulfurized at 66, such as by treatment with an aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH4OH), or ammonia, or other suitable chemicals such that the resulting desulfurized lead paste contains substantially sulfur-free lead components (e.g., Pb, PbO, PbO2, and Pb(OH)2) but no lead sulfate (PbSO4). At 68, the desulfurized lead paste can be combined with electrolyte and auxiliary chemicals to form a slurry mixture (or, in an alternative embodiment, a slurry solution). This slurry can then be introduced into an electrolytic cell at 70, and solid-state electrolysis (or, in an alternative embodiment, typical solution-based electrolysis) can occur at 72.

[0045] Once electrolysis is complete, the liquid components (which may include auxiliary chemicals or their residues) can then be drained first at 74, and the remaining solid components resulting from the electrolysis (which may be in the form of a "sponge lead" solid impregnated with the residual liquid components) can also be removed at 76, or in an alternative embodiment, the liquid and solid components can be simultaneously removed from the electrolytic cell. At 78, the "sponge lead" solid component, which substantially comprises pure lead (Pb), can be pressed to remove nearly all remaining liquid components ("residue") and form a substantially pure lead brick. The lead brick can then be melted at 80 to remove nearly all remaining amounts of non-lead components and other minor impurities, which melting occurs (at a temperature much lower than that required for melting) to further refine the lead brick and form a near-pure lead ingot for output.

[0046] In particular, elements 70-76 shown as electrolytic process group 82 in Figure 1B are performed utilizing various embodiments of an electrolytic cell described in more detail below, although nothing herein limits the use of such embodiments to lead recycling or just this portion of a lead recycling process; to the contrary, other additional uses of such embodiments are also contemplated by such embodiments. For example, various embodiments disclosed herein may be used to further process dross removed during melting 80, including, but not limited to, the processing described with respect to Figure 1A above.

[0047] Figure 1C is a modified process flow diagram 60' of the process 60 shown in Figure 1B to further illustrate in greater detail the separate treatment of other recyclables 64 and dross processing 92, representative of various embodiments disclosed herein. In Figure 1C, at 84, battery acid, typically sulfuric acid (H2SO4), is neutralized and output from the system. At 86, plastic is cleaned and output from the system, along with any lead residue (typically lead monoxide) recovered from the surface of the plastic, which is combined with lead paste to be desulfurized. Similarly, at 88, the separator is cleaned and output from the system, along with any lead residue (typically lead monoxide) recovered from the surface of the plastic, which is combined with lead paste to be desulfurized. The grid metal can then be "cleaned" at 90 of any recoverable non-lead components, such as lead alloys from the grid being output (discarded or recycled) and its recoverable lead components, and finally, the pure lead (Pb) from the lead paste adhering to the grid can be transported at 80 for melting or directly to a melter for lead paste and other forms of lead oxide, for example, routed at 66 for further processing.

[0048] As previously disclosed herein, grids recovered from LAB grid metals are often constructed from a lead alloy containing lead (Pb) and antimony (Sb), i.e., lead-antimony (or antimony-lead). While the lead and antimony from the alloy can be separated using known processes to do so, thereby increasing the amount of elemental lead recovered and applicable to certain select embodiments disclosed herein, the need for recycled antimony-lead (i.e., lead alloy) for use in new grids for new batteries does not warrant separation of lead from antimony in such alloys, but instead warrants reuse of the lead-antimony as a recycled product separate from that disclosed for various other embodiments described herein. For those embodiments in which separation of elemental lead from antimony in the alloy is not required (leaving the alloy intact), this lead-antimony alloy can be melted by a recovery machine 90, from which it can be directed to the same melter used for melting in 80, or otherwise melted to form clean antimony-lead ingots. Specific embodiments directed to the recovery of lead alloys and specific processing of grid metals are disclosed in more detail later in this specification.

[0049] Also shown in FIG. 1C is an approach whereby the dross resulting from the melting at 80 is mechanically separated at 92, with the lead monoxide (PbO) resulting from the mechanical separation being added directly or indirectly to a subsequent batch of desulfurized lead paste at 68 for reprocessing, while the elemental lead (Pb) resulting from the mechanical separation is added to a subsequent batch of sponge lead that is melted at 80 (disclosed in more detail later herein).

[0050] Electrolyzer cell with horizontal cathode Disclosed herein is an electrolytic cell cell including a horizontal cathode from which a horizontal anode hangs. This horizontal cathode can form the base of an electrolytic cell compartment into which an active material and electrolyte mixture, e.g., in the form of a slurry, can be introduced, held, and processed. The horizontal anode can be suspended above the cathode at the top of the electrolytic cell compartment such that the anode physically engages the top surface of the active material and electrolyte mixture held by the electrolytic cell compartment, while the cathode naturally engages the bottom surface of the active material mixture held within the electrolytic cell compartment. The anode can also include small openings in the form of vents, grooves, holes, etc. (sometimes referred to herein simply as "breathing holes") across its surface to allow gaseous oxygen (O) and / or other gaseous substances resulting from electrolysis to harmlessly escape (instead of being trapped below the anode and creating a current resistance).

[0051] Accordingly, various embodiments disclosed herein may be directed to and / or utilize electrolytic cells including a horizontal cathode positioned below a suspended anode for the purpose of conducting electrolysis on a metal-containing mixture or solution. In some such embodiments, the horizontal cathode may include a bottom of a compartment for containing the mixture or solution of metal components, electrolyte, and / or auxiliary chemicals; a horizontal anode for engaging an upper surface of the mixture or solution within the compartment; a gate corresponding to one sidewall of the compartment for facilitating removal of end products from the mixture or solution; and / or a removal mechanism for facilitating removal of end products of the mixture or solution from the compartment (and the surface of the horizontal cathode) through the gate. While certain embodiments disclosed herein are specifically directed to use in recycling lead-acid batteries (LAB) without smelting, nothing herein is intended to limit various embodiments to only LAB recycling or lead recovery; instead, various embodiments disclosed herein may be applied to a variety of different electrolysis operations.

[0052] For these various embodiments, and when combined with the use of additional auxiliary chemicals added to the active material and electrolyte slurry mixture (discussed further below), an electrical DC current can then be passed from the cathode to the anode through the active material and electrolyte mixture to produce the desired end product, and the desired end product can precipitate on the surface of the cathode. (For certain such embodiments, the end product can be pure lead in a sponge-like form that retains a portion of the electrolyte and / or auxiliary chemicals.) More specifically, the electrical DC current effectively causes the reduction of metal ions in the active material to separate from their counterions (e.g., oxides and hydrogen ions, which can then form water (HO) and gaseous oxygen (O)), where the metal in its pure form is then attracted and precipitates onto the horizontal cathode surface due in part to gravity (the metal is heavier than the other components in the slurry) and in part assisted by natural ionic convection that occurs in the mixture during electrolysis.

[0053] Once electrolysis is complete, for some such embodiments disclosed herein, the electrolytic cell compartment can further include an openable side for removing the electrolyte (including auxiliary chemicals and any additional HO produced during electrolysis) and the end-product metal. Initially, this openable side can first only be partially opened to allow the pure liquid components, i.e., most of the remaining electrolyte, auxiliary chemicals, and any additional water (HO) produced during electrolysis, to exit the electrolytic cell compartment and, for certain embodiments, be channeled through a small channeling groove at the base of the openable side. In some embodiments, this channeling groove can then be moved to a storage position away from the openable side (e.g., below the electrolytic cell compartment) after the liquid components have drained through the openable side of the electrolytic cell compartment.

[0054] After the liquid component is drained, or in an alternative embodiment, without first draining the liquid component separately, the openable side can be fully opened to allow more solid components, i.e., the final product metal plus any residual liquid components adhering thereto, to be physically removed from the electrolytic cell compartment. For selected embodiments, this removal can be performed by a vertical scraping mechanism that extends across the width of the electrolytic cell compartment and originates from the opposite side of the openable side, with the scraping component physically contacting and gently scraping the entire cathode surface and the adjacent side of the electrolytic cell compartment, but operating just below (and without physically contacting) the anode surface. In this manner, the scraping mechanism can operate to push more solid components out of the electrolytic cell compartment into a collection receptacle or onto a transport mechanism (e.g., a conveyor belt) for further processing.

[0055] In this way, various embodiments disclosed herein can overcome the drawbacks of existing approaches to solid-state electrolysis discussed above by: (1) eliminating the need to dry-paste the active material onto the cathode, saving time and labor; (2) completely avoiding the accumulation of water absorbed by the dry-pasted active material during electrolysis, which would otherwise interfere with the production of the resulting desired end product; and / or (3) facilitating the removal of end product buildup at the cathode, as the flat surface of the cathode facilitates the scraping action (discussed above) and auxiliary chemicals can help prevent the end product from solidifying or adhering to the cathode.

[0056] Furthermore, for various embodiments disclosed herein, multiple electrolytic cell cells of the type described herein can be stacked vertically with appropriate spacing between each electrolytic cell cell, and each electrolytic cell cell can share a single vertical drop space for the final product extruded from the multiple electrolytic cell cells in a single collection receptacle or on a single transport mechanism. Furthermore, several vertical stacks containing multiple electrolytic cell cells can be arranged in a row and further share a single elongated collection receptacle or a single elongated transport mechanism. Furthermore, multiple rows of vertical stacks can be arranged such that the produced final products are consolidated for continuous processing.

[0057] In particular, apart from the disclosures made herein, applicants have discovered that achieving the electrolytic effect described herein depends on the utilization of certain specific chemicals mixed into the slurry along with the electrolyte and active material. The present application is not directed to the composition of any of these discovered chemicals, but the various embodiments disclosed herein are in no way limited to the use of any particular chemical additives, whether proprietary or proprietary (or widely used and well known for that matter).

[0058] Figure 2A provides a perspective view of an electrolyzer cell 100, representing various embodiments disclosed herein. Figure 2B provides a perspective view of the anode 110 and interior blowout of the electrolyzer cell 100 of Figure 2A, representing various embodiments disclosed herein. For convenience, Figures 2A and 2B may be collectively referred to herein as Figure 2.

[0059] 2, the electrolyzer cell 100 may include an anode 110 suspended above a horizontal cathode 120 at a distance suitable for conducting electrolysis. The electrolyzer cell 100 may also include a vertical containment surface 122 and at least one gate 124, which together with the horizontal cathode 120 form and provide an electrolyzer compartment 126 into which a mixture of active material and electrolyte, for example in the form of a slurry, may be introduced, held, and processed. The vertical containment surface 122 and gate 124, or at least their interior surfaces relative to the contents of the electrolyzer compartment 126, may be electrically non-conductive.

[0060] As shown in the figure, the anode 110 may be configured as a horizontal anode, although other forms of anodes may also be utilized, such as, for example, a series of anode rods, strips, grids, or other structures capable of physically engaging the top surface of the electrolytic slurry mounted on the cathode. Nevertheless, the anode 110 may be suspended above the cathode 120 at the top of the electrolytic cell compartment 126 such that the anode physically engages the top surface of the active material and electrolyte mixture held by the electrolytic cell compartment, while the cathode naturally engages the bottom surface of the active material mixture held within the electrolytic cell compartment. For those embodiments featuring a horizontal anode, the anode 110 may also be provided with small openings or vents 114 (i.e., "breathing holes") across its surface to allow gaseous oxygen (O) resulting from electrolysis to harmlessly escape (instead of being built under the anode). The anode 110 may also include an opening 112 through which the electrolytic slurry may be installed within the electrolytic cell compartment and on the horizontal cathode 120 in a quantity sufficient to simultaneously physically engage the upper surface of the suspended anode 110, thereby completing a circuit for electrical current to flow between the cathode 120 and the anode 110 for purposes of electrolysis.

[0061] The electrolyzer cell 100 may further comprise a removal mechanism 160. For various embodiments, this removal mechanism 160 may include a vertical surface extending across the width of the electrolyzer compartment 126 and beginning opposite the gate 124, which is capable of physically contacting and gently rubbing the entire surface of the cathode 120 and the adjacent sides of the electrolyzer compartment 126, and operating below the surface of the anode 110. The removal mechanism, or at least the portion thereof exposed to the contents of the electrolyzer compartment 126, may be electrically non-conductive.

[0062] Figure 3A provides a cutaway side view of the electrolyzer cell 100 of Figures 2A and 2B, representing various embodiments disclosed herein, in an initial, ready-to-use configuration for conducting electrolysis. As shown in Figure 3A, the electrolyzer compartment 126 is empty but ready to be filled, with the removal mechanism 160 in the set position and the gate 124 closed. In this configuration, electrolytic slurry can then be deposited into the electrolyzer compartment 126 and onto the horizontal cathode 120 via the slurry line 144 extending through the opening 112 in the anode 110. Figure 3A also shows a conveyor belt 170, with a receiving side 172, disposed directly below the gate 124 as a conveying mechanism for use during removal of the contents of the electrolyzer compartment 126 after electrolysis is completed.

[0063] 2A and 2B (and FIG. 3A) after being filled with an electrolyte 150 for electrolysis, representing various embodiments disclosed herein. As shown in FIG. 3B, the electrolyte 150 includes a mixture of active material 130 and electrolyte 140, as well as auxiliary chemicals, interspersed therein. The bottom surface of the electrolyte 150 physically engages (i.e., is in physical contact with) the horizontal cathode 120, while the top surface of the electrolyte (specifically, its electrolyte component) physically engages the anode 110. (For various embodiments, sufficient electrolyte can be included in the electrolyte to form the top surface of the electrolyte to prevent solid material contact between the cathode and anode from creating an electrical short that could prevent the cathode plate from reducing lead ions from the compound.) An electric current can then be applied to the electrolyte 150 via the anode 110 and cathode 120, and an electrical circuit is completed by the mobile ions in the electrolyte 140, causing electrolysis in the electrolyte 150 in response.

[0064] 3C provides a cutaway side view of the electrolyzer cell 100 of FIGS. 2A and 2B (and FIGS. 3A and 3B), representative of various embodiments disclosed herein, after electrolysis has been performed and the liquid component 142 has been drained from the electrolysis compartment 126 by opening the gate 124 to a first position that provides sufficient space for the liquid component 142 to pass from the electrolyzer compartment 126 onto the conveyor belt 170 for collection, while the desired end product 132 of the electrolysis remains on the horizontal cathode 120 awaiting its removal from the electrolyzer compartment 126.

[0065] 3D provides a cutaway side view of the electrolytic cell 100 of FIGS. 2A and 2B (and FIGS. 3A, 3B, and 3C), representing various embodiments disclosed herein, after the final product 132 resulting from electrolysis has been removed from the surface of the horizontal cathode 120 and from the electrolysis compartment. As shown in FIG. 3D, the gate 124 has been moved to a second, fully open position, and the removal mechanism 160 has traversed the interior of the electrolytic cell 100 to remove the final product 132 from the electrolytic cell 100 onto a conveyor belt 170. With the removal mechanism 160 in this deployed position and the gate 124 fully open as shown, the empty interior of the electrolytic cell 128 is no longer the electrolysis compartment 126, but will again become the electrolysis compartment 126 after the removal mechanism 160 is returned to its original position and the gate 124 is closed (e.g., as shown in FIG. 3A). For convenience, Figures 3A, 3B, 3C, and 3D may be collectively referred to herein as Figure 3.

[0066] Figure 4A provides a perspective view of a vertical stack 102 of electrolyzer cells 100, representing various embodiments disclosed herein. As shown in Figure 4A, multiple electrolyzer cells 100 can be oriented vertically on a single conveyor belt 170 (further distinguished in the figure by block movement arrows) to increase overall capacity, minimize floor space (or footprint), and increase utilization of the conveyor belt 170 (and minimize construction of the conveyor belt 170).

[0067] 4B provides a perspective view of a siding 104 including multiple vertical stacks 102 of electrolyzer cells 100, representing various embodiments disclosed herein. As shown in FIG. 4B, multiple stacks can be oriented linearly on a single conveyor belt 170 to further increase overall capacity, while again increasing utilization of the conveyor belt 170 (and minimizing build-up of the conveyor belt 170), as opposed to the need for individual conveyor belts for each stack 102. Furthermore, for certain embodiments, multiple stacks 102 can be oriented on either side of the conveyor belt 170 to form a double siding (not shown).

[0068] 4C provides a perspective view of a parallel array 106 of multiple lateral lines 104, each comprising multiple stacks 102 of electrolyzer cells 100, representative of various embodiments disclosed herein. As shown in FIG. 4C, the multiple lateral lines 104 and their corresponding conveyor belts can be aligned to form a three-dimensional array 106 of electrolyzer cells that feed a unified cross-conveyor belt 176. Furthermore, for certain embodiments, the conveyor belts 170 from the multiple lateral lines 104 can be oriented on either side of the cross-conveyor belt 176 to form a double array (not shown). Furthermore, the particular height, length, and width of such a parallel array 106 can be configured to optimally fit into nearly any three-dimensional space, although alternative or additional conveyor belt configurations may be required.

[0069] For all of the various embodiments disclosed herein, alternative embodiments are contemplated in which the horizontal cathode is instead a horizontal anode and the suspended anode is instead a suspended cathode. Additionally, each step of the process performed by the various embodiments disclosed herein may be performed and controlled by a processing unit or other computing environment, including (but by no means limited to) timing each step of operation, coordination between different electrolyzer cells, slurry lines, conveyor belts, etc., and variations in time and charge utilized throughout the electrolysis process, as well as receiving and reacting to feedback from electrical resistance and other detectable events from the ongoing electrolysis.

[0070] Electrolytes and Supporting Chemicals As previously disclosed herein, sodium hydroxide (NaOH), as well as potassium hydroxide (KOH), and the like, can be used as electrolytes for subsequent electrolytic treatment (e.g., electrolysis) of the lead paste, in which case the resulting lead slurry is a mixture of desulfurized lead paste and electrolyte (not, in the chemical sense, a solution thereof). Note that this approach deviates from the typical electrolytic treatment of lead paste dissolved and suspended in an electrolyte solution, which does not require auxiliary chemicals, whereas the electrolytic treatment of a mixture benefits from auxiliary chemicals.

[0071] Also, as known and understood by those skilled in the art, lead monoxide (PbO) can be removed from the dross by the use of sodium hydroxide (NaOH), which acts to dissolve the lead monoxide (PbO) and form a solution that is effectively separated from other solid impurities, including the dross. Once the dissolved lead-containing solution has been separated from the solid dross residue, i.e., after the solid residue has been filtered from the solution, the lead monoxide (PbO) solution can be further processed to recover pure lead (Pb) therefrom.

[0072] Figure 5A is an annotated chemical diagram of the molecular structures of lead monoxide (PbO) 502, lead dioxide (PbO2) 504, and lead hydroxide (Pb(OH)2) 506 (collectively, "lead oxide components" or "lead oxides"). Figure 5B is an annotated chemical diagram of the molecular structures of lead sulfate (PbSO4), shown for clarity with 508a and without 508b a bonded charge (i.e., a lead (Pb) atom juxtaposed with two oxygen atoms having single bonds to sulfur atoms). As previously mentioned, lead paste derived from recycled LAB typically contains pure lead as well as portions of lead monoxide, lead dioxide, and lead sulfate.

[0073] Lead monoxide (PbO), also commonly called lead(II) oxide, has an oxidation state of +2. PbO is formed during the discharge of the LAB as a proton-electron mechanism of PbO2 reduction. (Note that the positive plate of the LAB is composed of PbO2 and the negative plate of the LAB is composed of pure lead, Pb.)

[0074] Lead dioxide (PbO2), commonly called lead(IV) oxide, has an oxidation state of +4. The positive plate of the LAB is composed of PbO2, while the negative plate of the LAB, in contrast, is composed of pure lead, Pb.

[0075] Lead hydroxide (Pb(OH)2), commonly referred to as lead(IV) oxide or, less precisely, "lead hydrate" (this latter term is also used to refer to Pb(H2O)2), has an oxidation state of +2. Pb(OH)2 results from the interaction between the PbO2 plates in the LAB and the aqueous sulfuric acid (H2SO4) solution of the LAB (which also results in PbSO4). As previously explained herein, lead sulfate (PbSO4) is converted to lead hydroxide (Pb(OH)2) during desulfurization, which occurs prior to electrolytic processing.

[0076] In order for the electrolysis process to successfully recover elemental lead (Pb) from the lead oxide present in the lead slurry prepared for solid-state electrolysis, one or more auxiliary chemicals can be added to the lead slurry mixture (including the electrolyte and lead oxide components) prior to electrolysis. During electrolysis, these auxiliary chemicals will effectively allow the oxygen (O) and / or hydroxide (OH) molecules in the lead oxide to separate from the lead (Pb) and combine to form gaseous O (which can then dissipate from the mixture into the ambient air) and / or water (H2O) (which can then remain in the mixture and be pressed or boiled in subsequent processing of the resulting elemental lead (Pb)).

[0077] In particular, for the electrolysis process to successfully recover elemental lead (Pb) from lead monoxide (PbO) in a lead slurry during solid-state electrolysis, various embodiments disclosed herein utilize one or more PbO-specific auxiliary chemicals (hereinafter referred to as "MoXX") that are added to the lead slurry mixture (including the electrolyte and PbO components) prior to electrolysis. When AXC is included as an auxiliary chemical mixed with the lead paste and electrolyte for solid-state electrolysis, during electrolysis, AXC effectively assists the oxygen (O) in the lead monoxide (PbO) to separate from the lead (Pb) and combine with other oxygen (O) to form gaseous O (which can then dissipate from the mixture into the ambient air) or combine with hydrogen (H) and other oxygen (O) (usually in the form of hydroxide (OH) anions) to form aqueous water (HO) in the mixture. The latter of these by-products can then be pressed or boiled in subsequent processing of the resulting elemental lead (Pb).

[0078] Accordingly, various embodiments disclosed herein may be directed to recovering specifically pure lead (Pb) from lead monoxide (PbO) present in paste derived from LAB. Various such embodiments are directed to a method for recovering near-pure elemental lead (Pb) from a material containing lead monoxide (PbO) by combining the material with an electrolyte and at least one auxiliary chemical to form a slurry, the slurry being a mixture of the material and the electrolyte, where the electrolyte does not dissolve the lead monoxide in the material; subjecting the slurry to solid-state electrolysis to convert the lead monoxide to elemental lead in a spongy form; pressing the spongy lead to substantially remove the electrolyte; dissolving the spongy lead to produce near-pure elemental lead and dross; and removing the dross from the near-pure elemental lead.

[0079] Recovery of lead oxide from non-lead components As previously disclosed and / or described herein, LAB designated for recycling is first physically reduced (or "shredded") and separated / divided into five major subcomponents: battery acid (if present), plastic, separator, grid metal, and lead paste. The battery acid, typically sulfuric acid (H2SO4), can be output to an acid neutralizer, and the lead paste can be immediately directed to a primary lead recovery operation. However, the other components, i.e., plastic, separator, and grid metal, must first be "cleaned" and purified from any incorporated or adhering lead oxide (often in the form of residual battery paste) before they can be further processed and recovered. Unfortunately, as is well known and readily recognized by those skilled in the art, cleaning these components, particularly absorbent glass mat (AGM) separators, is notoriously difficult, and as little as 0.5% of the lead oxide remains unrecovered from such components, often re-entering the environment as lead contamination.

[0080] To address these challenges, various embodiments disclosed herein are directed to systems, methods, processes, and / or chemical compositions for recovering lead oxide from the non-lead components of recycled LAB, specifically from its plastic, separator, and grid metal components. Some and various embodiments disclosed herein feature new processes, innovative electrolytic cell designs, and / or novel utilization of auxiliary chemicals necessary for the successful subsequent electrolytic processing of lead oxide to convert it to near-pure elemental lead.

[0081] 6A is a partially modified block diagram 10′ illustrating the major components of an exemplary cleaning subsystem, based in part on the system 10 shown in FIG. 1A , for recovering lead oxide from non-lead components (NLC) during recycling of lead-acid batteries (LAB) 12, representing various embodiments disclosed herein. In FIG. 6A , the cleaning subsystem 10′ includes, among other components, a plastic washer 40, a separator purifier 22, and an LAB shredder operably coupled to a metals recovery machine 20 (including a metal washer 20′), all of which are operably coupled to an electrolytic process 28′ (representing most of the blocks in FIG. 1A that are not individually shown in this FIG. 6A ).

[0082] 6B is a partially modified process flow diagram illustrating an exemplary washing process, based in part on the approach shown in FIGS. 1B and 1C, for recovering lead oxide from non-lead components (NLC) during lead-acid battery (LAB) recycling, representing various embodiments disclosed herein. In FIG. 6B, the LAB are received at 50 and broken down into their separate components: battery acid (if present), which is neutralized at 52; plastic, which is washed at 54 and recycled at 54'; AGM separator, which is cleaned (washed) at 56 and recycled or reused at 56'; lead paste, which is electrolytically processed at 94 (to produce near-pure lead (Pb) 48 using any of the processes previously disclosed herein); and grid metal, which is washed at 58 and the remaining antimony lead (and the lead paste still adhering to it) is processed at 58' to further recover target metal and / or alloy (lead paste and / or clean lead-antimony (Pb-Sb)), which will be described in more detail in the next section.

[0083] Accordingly, various embodiments disclosed herein are directed to methods and / or systems for removing lead oxide from non-lead components. More specifically, various embodiments disclosed herein are directed to a method for recovering lead oxide from non-lead components (NLC) during lead-acid battery (LAB) recycling, the method comprising: immersing and agitating the NLC in a solution containing at least one auxiliary chemical to separate the lead oxide from the NLC and forming a resultant mixture containing the solution and lead oxide; removing the NLC from the resultant mixture; washing the NLC with water to remove any adhering resultant mixture; and subjecting the mixture to an electrolytic process to deoxidize the lead oxide and thereby produce elemental lead (Pb) therefrom. This approach can also be utilized to pre-clean grid metal before further processing, as described in more detail in the next section.

[0084] Recovery of lead oxide and lead alloys from grid metals To maximize the available surface area and thereby increase the efficiency of electrical current, one or more grid metal pairs (each a "plate") are commonly used in LABs for both the positive and negative electrodes in the battery. Typically, these plates include a metal grid (usually a lead alloy) onto which a lead-based paste (which may include lead oxide, sulfuric acid, and water) is applied and cured to cause it to adhere to the metal grid and become the electrochemically active material (the "active material") for such plates / electrodes upon initial charging ("formation"). In a fully charged state, the active material for the positive plate may include primarily lead dioxide, whereas the active material for the negative plate may include primarily elemental lead, while in a fully discharged state, the active material for both the positive and negative plates may include primarily lead sulfate.

[0085] In particular, pure lead is too soft and malleable to form metal grids for both the positive and negative plates; instead, lead alloys such as lead antimony (PbSb) are used to provide sufficient grid rigidity while also enhancing current flow. Additionally, the grids may be physically structured for improved mechanical strength and improved current flow through different grid patterns. One or two thin "cloths" may also be installed on the grid to more evenly distribute the weight of the active material.

[0086] While lead-antimony alloys can provide the necessary rigidity for grid structures, alternatives such as lead-calcium grid alloys and lead-selenium grid alloys, which themselves still contain relatively small amounts of antimony compared to lead-antimony alloys, offer metallurgical improvements that provide enhanced grid strength for certain LAB applications and uses, which in turn allows the grid to carry more weight (i.e., more active material), thereby allowing for thicker plates and improved battery life given the additional active material available, although they have their own specific drawbacks that limit their widespread use to specialized applications. Nevertheless, the lead alloys used for grids, unlike the lead oxides present in the active material, benefit from being recovered separately in LAB recycling.

[0087] Stated differently, the electrodes of a lead-acid battery (LAB) typically include a metal frame ("grid") coated with a lead-based paste ("paste"), the former being composed of a relatively hard, conductive lead alloy (e.g., lead antimony), while the latter typically includes lead oxide and lead sulfate coated on (and strongly adhered to) the exposed surface of the lead alloy grid. Additionally, one or two thin "cloths" may be installed on the surface(s) of the grid and paste combination to promote and maintain uniform weight distribution. This assembly, with or without the cloth, is broadly referred to herein as the "grid metal" of the LAB.

[0088] When recycling LABs, it is desirable to recover the lead alloy separately from the lead oxide component of the grid metal (e.g., lead paste). For example, recycling LABs using a high-temperature smelting process in which the lead alloy and lead oxide are smelted and mixed together results in impure lead as the output, which then requires extensive additional refining and / or alloying treatments that are time-consuming and energy-intensive. Similarly, recycling LABs using an electrolysis process is similarly problematic, as the presence of the lead alloy in the lead slurry (including the electrolyte) can interfere with the electrolysis efficiency, resulting in impure lead as the output.

[0089] To address these shortcomings, various embodiments disclosed herein are directed to separating and separately processing the lead paste from the lead alloy to recover pure elemental lead from the former while also recovering clean lead alloy that can be readily reused, for example, in the manufacture of new lead-acid batteries. For some of these embodiments, the lead paste that would otherwise adhere to the lead alloy grids is chemically loosened via immersion in a proprietary solution and then roughly agitated (or "hammered") in a rotating, baffled, barrel-like drum to facilitate complete separation of the lead paste from the crushed lead alloy components.

[0090] FIG. 7A is a modified process flow diagram 700 illustrating an exemplary process for separating lead paste adhering to crushed lead alloy components to facilitate recovery of elemental lead from the former and clean the lead alloy from the latter, in a manner representative of various embodiments disclosed herein. As shown in FIG. 7 and for some embodiments disclosed herein, following battery shredding and recovery / removal of battery acid, plastic, and separator, the remaining chunks of lead paste and grid metal (“chunk”) can be further processed to physically separate the grid metal (lead alloy) from the lead paste (lead oxide). At 702, the chunks are mixed with a proprietary solution containing proprietary chemicals to create a chunk mixture. At 704, the chunk mixture is then introduced into a paste separation unit (PSU) drum. This PSU drum may be a laterally rotatable drum containing one or more baffles, and as the drum rotates, a hammering effect (“hammering”) is created on the chunk mixture to separate the lead paste from the crushed lead alloy grid components at 706. The unique chemicals contained in the unique solution serve to loosen the lead paste on the lead grid and facilitate the desired physical separation of the lead paste from the lead alloy during hammering.

[0091] After the hammering is complete, any cloth that was included in the mass that was stripped of any lead paste and lead alloy during hammering is removed at 708. For certain embodiments, the proprietary solution allows the lead paste and lead alloy to sink to the bottom of the mixture, while the cloth floats to the top of the mixture, thereby allowing the cloth to be removed by skimming it from the top of the mixture. At 710, the hammered mass, which is still a mixture of lead paste, lead alloy, and proprietary solution, is removed from the PSU drum. Notably, the lead paste is no longer attached to the crushed lead alloy component, but the lead paste and crushed lead alloy component are still mixed together in the proprietary solution.

[0092] Also, at 710, the hammered mass may then be received by an alloy separation unit (ASU) including a holding vessel, a slurry tank positioned vertically below the holding vessel, and an alloy press. This holding vessel may be a vibrating vessel further comprising a sieve-like bed or base through which the lead paste and proprietary solution can pass but not the crushed lead alloy components. Then, at 712, the vibrating vessel vibrates the received hammered mass to facilitate gravity-assisted separation of the lead paste and proprietary solution through the sieve-like bed / base into the slurry tank, while the crushed lead alloy components remain in the holding vessel.

[0093] At 714, the crushed (but in this case clean) lead alloy components, free of lead paste and substantially free of proprietary solution, can be removed from the holding vessel and pressed through an alloy press to produce clean alloy pellets, which contain clean lead alloy ready for immediate reuse in LAB grid manufacturing and / or other uses, while at 716 the lead paste and proprietary solution mixture (in this case, alloy-free lead slurry) can be removed from the slurry tank and further processed to recover pure elemental lead by smelting, electrolysis, or other means.

[0094] Of course, those skilled in the art will understand and appreciate a variety of alternative embodiments that naturally and inherently arise from the foregoing disclosure. These include, but are not limited to, the PSU and ASU operations being separated and performed independently, in different sequences, or repetitively without the other's operations, and / or one processing an input that is not derived from or derived for use by the other. The PSU substantially discharges its own solution and separated lead paste (as a lead slurry) from the post-hammered mixture, and for certain embodiments, this lead slurry is further processed (immediately or eventually) to recover pure elemental lead by smelting, electrolysis, or other means. The substantially clean, crushed lead alloy components are separately removed from the drum for further processing. Here, further processing involves pressing and / or directly utilizing the substantially clean lead alloy, utilizing water in a proprietary solution, removing water from the resulting hammered mass, from the discharged lead paste mixture, and / or from the proprietary solution in the PSU and / or ASU, or from the alloy pressing in the ASU, and recycling and reusing the proprietary solution in one or more subsequent masses. The proprietary solution used in the PSU and ASU may be the same or alternatively different for each. The hammered mass received by the ASU contains only lead paste and crushed grid metal components, and no proprietary solution. The mass (or other input) may be washed before being processed by the PSU, or the hammered mass (or other input) may be washed before being processed by the ASU. The slurries from the PSU and ASU may be mixed and processed together to recover elemental lead, or alternatively, may be processed separately. The grid metal may be separated from the batteries before being crushed and processed separately from the other components, etc., without limitation. Furthermore, as used herein, the term "agitating" is intended to have a broad meaning that includes both hammering and / or vibration as these terms are disclosed or utilized herein.

[0095] 7B is a modified block diagram 700′ illustrating the major components of an exemplary paste separation unit (PSU) 720, representative of various embodiments disclosed herein. As shown in FIG. 7B, the PSU 720 may include a laterally rotatable drum 722 that includes one or more input / output openings 724 (and one or more doors 724′) through which material may be received or removed, and one or more internal baffles 726 that, when the drum 722 is rotated (via a rotation motor, not shown), move the chunk mixture within the drum 722 in such a manner to create a hammering effect (“hammering”) on the chunk mixture and promote physical separation of the lead paste from the crushed lead alloy grid components within the mixture. In effect, the baffles promote rotation of the electrode material, and with adjustments to the rotational speed of the drum, ever-changing portions of the mass are rotated to the top of the drum (due to rotational inertia assisted by the scooping action of the baffles) and then, under the action of gravity, fall downward onto other portions of the mass below (the falling solid electrode material hammering the solid electrode material at the bottom). For certain embodiments, the PSU drum 722 may also include a hatch 732 (shown closed) through which the floating fabric may be removed from the surface of the mass after hammering, the fabric being stripped from any lead paste or crushed lead alloy components during hammering (the latter sinking to the bottom of the mixture while the fabric floats on top).

[0096] For some embodiments, the PSU drum 722 may further include a drain 730 through which the proprietary solution and lead paste components are removed from the PSU 722 after hammering of the mass by the influence of gravity, additional rotation of the drum, and / or other means, while the crushed lead alloy components are largely or completely unable to pass through the drain 730 and may be separately removed from the PSU drum 722 in a substantially clean form, free of the lead paste and proprietary solution after hammering and draining, via one or more input / output openings 724. In some embodiments, the PSU 720 may further include an alloy press 728 for pressing the lead alloy removed from the PSU drum 722 into pellet form (pellets). Selected embodiments may also include a post-hammer wash 734 (not shown) for washing the lead alloy one final time to remove any residual lead paste or proprietary solution therefrom before pressing the lead alloy into pellets.

[0097] For various embodiments, the baffles 726 within the drum 722 may be fixed within the drum 722 (and may rotate with the drum 722), while for certain other embodiments, the baffles 726 may not be fixed, may not rotate within the drum 722, may rotate differently from the drum 722, may rotate in the opposite direction to the drum 722, or may exhibit a motion other than simple rotation. For embodiments having a baffle 726 that is fixed within the drum 722 (and rotates with the drum 722), the baffle 726 may be oriented in several different configurations, may be attached to an inner cylindrical surface of the drum 722, may be attached to a central axis running through the drum 722, or both. Similarly, the drum 722 may have any number of baffles 726, from one to many, oriented in any configuration. Indeed, any number and orientation of baffles 726 within drum 722 is contemplated as a natural variation of several different embodiments disclosed herein, which can aid in agitating and hammering the mass within drum 722 when rotated at any speed, slow or fast. PSU 720 can also include a press for producing pressed shapes (such as pellets) from lead alloys or other metals.

[0098] Additionally, for certain selected embodiments, the interior of drum 722 may further include components necessary for some form of electrolytic treatment of the mass within the drum before, during, and / or after hammering to further facilitate separation of the lead paste adhering to the lead alloy, which electrolytic treatment may be an adaptation of the solid-state electrolytic process previously disclosed herein but utilized for this specific purpose herein. For such electrolytic treatment, proprietary chemicals in proprietary solutions may act as auxiliary chemicals to facilitate such separation, or auxiliary chemicals may be distinct from the proprietary chemicals and specifically added to the mixture to facilitate the electrolytic treatment.

[0099] FIG. 7C is a simplified block diagram 700″ showing a side cutaway view of the major components of an exemplary alloy separation unit (ASU) 740, representative of various embodiments disclosed herein. As shown in FIG. 7C, the ASU 740 can include a holding vessel 742, a slurry tank 744 that can be positioned vertically below the holding vessel 742, and an alloy press 728′. The holding vessel 742 can be a vibrating vessel, i.e., a vessel that uses mechanical motion to vibrate, rock, agitate, or otherwise cause movement (“mass transfer”) within and between hammered mass components or other mixed inputs, which may be referred to herein, for example, simply as “vibration,” and which ostensibly include two or more different components (“mass inputs”), causing lighter components to rise and heavier components to sink, and / or liquid components and components suspended in liquid to exit the holding vessel 744 via gravity assistance.

[0100] To allow for such drainage, the holding vessel 742 may further include a sieve 746, i.e., a sieve-like bed or base through which lead paste, proprietary solutions, water, and the like may pass, for example, from the holding vessel 742 into the slurry tank 744, but through which crushed lead alloy components cannot pass and which may be removed via a separate output 748 (as shown) which may also function as an input for introducing the mass into the holding vessel, or the output 748 may also be separated from such input.

[0101] For certain embodiments, the ASU 740 may also include a press 728' for pressing the resulting lead alloy into lead alloy pellets, effectively removing any residual liquid components that were not previously drained. Additionally, for selected embodiments, the ASU 740 may also include an auxiliary washer 20'' for additionally washing the lead alloy resulting from the operation of the holding vessel to remove any residual lead alloy, proprietary solutions, etc. from the resulting lead alloy prior to pressing. These and other variations not specifically described herein will nevertheless be readily apparent to and understood by those skilled in the art as essentially disclosed herein.

[0102] Furthermore, for certain selected embodiments, the interior of holding vessel 742 may further include components necessary to perform some form of electrolytic treatment of the hammered mass (or other mass or equivalent) disposed within the drum (preferably before or during vibration) to further facilitate separation of the lead paste adhering to the lead alloy, which electrolytic treatment may be an adaptation of the solid-state electrolytic process previously disclosed herein but utilized herein for this specific purpose. For such electrolytic treatment, proprietary chemicals in proprietary solutions may act as auxiliary chemicals to facilitate such separation, or auxiliary chemicals may be distinct from the proprietary chemicals and specifically added to the mixture to facilitate the electrolytic treatment.

[0103] In particular, for certain alternative embodiments, features of PSU 720 and ASU 740 may be combined into a single unit, e.g., drum 722 may be the same as holding vessel 742, the "vibration" of ASU 740 may be generated by rotation of drum 722, drain 730 may include sieve 746, and / or alloy press 728 may also be press 728' and be the same press used after electrolytic processing of lead paste or other lead slurry. While described as separate components for convenience, it is not intended herein to limit PSU 720 and ASU 740 to separate embodiments or components, but instead, any combination of features between the two and / or with features otherwise disclosed herein for other embodiments is fully contemplated and disclosed herein explicitly, implicitly, and inherently.

[0104] Accordingly, various embodiments disclosed herein are directed to methods and / or systems for separating lead paste adhering to a lead alloy, which include mixing lead paste and a lead alloy with a solution to form a mixture, agitating the mixture in a manner sufficient that the lead paste is no longer physically adhered to the lead alloy, and removing the lead alloy from the mixture. In some such embodiments, the agitating may include rotary hammering of the mixture, the rotary hammering may be achieved at least in part through the use of a rotating drum, the rotating drum may include internal baffles that at least in part contribute to the rotary hammering, the rotational speed of the rotating drum may be maintained within a range that is substantially optimal for achieving rotary hammering of the mixture, and / or the range may be a rotational speed at which portions of the mass within the drum are lifted above a central axis of the drum and then dropped below the central axis, the mixture may further include a cloth adhering to the lead paste, and the agitation may cause the cloth to no longer adhere to the lead paste or lead alloy, the agitating may include vibrating a container containing the mixture, the vibration being sufficient to cause mass transfer within the mixture, the container may include a sieve through which the solution and lead paste can pass but not the lead alloy, and vibrating the container may at least in part facilitate passage of the solution and lead paste through the sieve. Certain embodiments may also include pressing the lead alloy into a pressed form. In selected embodiments, the solution may include at least one auxiliary chemical that at least partially reduces the adhesion of the lead paste to the lead alloy.

[0105] 8 is a block diagram of an exemplary computing environment that may be used in conjunction with exemplary embodiments and aspects such as those disclosed and described herein and with respect to the other figures presented herewith. This computing system environment is only one example of a suitable computing environment and is not intended to suggest any limitation as to scope of use or functionality.

[0106] Numerous other general-purpose or special-purpose computing system environments or configurations may be used. Examples of well-known computing systems, environments, and / or configurations that may be suitable for use include, but are not limited to, personal computers (PCs), server computers, handheld or laptop devices, multiprocessor systems, microprocessor-based systems, network PCs, minicomputers, mainframe computers, embedded systems, distributed computing environments that include any of the above systems or devices, etc.

[0107] Computer-executable instructions, such as program modules, may be used that are executed by a computer. Generally, program modules include routines, programs, objects, components, data structures, etc. that perform particular tasks or implement particular abstract data types. Distributed computing environments may be used where tasks are performed by remote processing devices that are linked through a communications network or other data transmission medium. In a distributed computing system, program modules and other data may be located in both local and remote computer storage media, including memory storage devices.

[0108] The various example logic, logic blocks, modules, and circuits described in connection with aspects disclosed herein may be implemented or performed using a general-purpose processor, a digital signal processor (DSP), an application-specific integrated circuit (ASIC), a field-programmable gate array (FPGA), an analog-to-digital converter (ADC) or other programmable logic device, discrete gate or transistor logic, discrete hardware components, discrete data acquisition components, or any combination thereof designed to perform the functions described herein. A general-purpose processor may be a microprocessor, but alternatively, the processor may be any conventional processor, controller, microcontroller, or state machine. A processor may also be implemented as a combination of computing devices, e.g., a combination of a DSP and a microprocessor, multiple microprocessors, one or more microprocessors in combination with a DSP core, or any other such configuration. Alternatively, at least one processor may include one or more modules operable to perform one or more of the steps and / or actions described above.

[0109] 8, an exemplary system for implementing aspects described herein includes a computing device, such as computing device 1000. In a basic configuration, computing device 1000 typically includes at least one processing unit 1002 and memory 1004. Depending on the exact configuration and type of computing device, memory 1004 may be volatile (such as random access memory (RAM)), non-volatile (such as read-only memory (ROM), flash memory), or some combination of the two. This basic configuration is indicated by dashed line 1006 in FIG. 8 and may collectively be referred to as the "computation" components.

[0110] Computing device 1000 may have additional features / functionality. For example, computing device 1000 may include additional storage (removable and / or non-removable) including, but not limited to, magnetic or optical disks, or tape. Such additional storage is illustrated in FIG. 8 by removable storage 1008 and non-removable storage 1010. Computing device 1000 typically includes a variety of computer-readable media. Computer-readable media may be any available media that can be accessed by device 1000 and may include both volatile and non-volatile media, and removable and non-removable media.

[0111] Computer storage media include volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information such as computer-readable instructions, data structures, program modules, or other data. Memory 1004, removable storage 1008, and non-removable storage 1010 are all examples of computer storage media. Computer storage media include, but are not limited to, RAM, ROM, electrically erasable read-only memory (EEPROM), flash memory or 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, or any other medium that can be used to store information and that can be accessed by computing device 1000. Any such computer storage media may be part of computing device 1000.

[0112] The computing device 1000 may include communication connection(s) 1012 that allow the device to communicate with other devices. The computing device 1000 may also have input device(s) 1014, such as a keyboard, mouse, pen, voice input device, touch input device, etc. It may also include output device(s) 1016, such as a display, speakers, printer, etc. All of these devices are well known in the art and need not be described in detail herein. The computing device 1000 may be one of multiple computing devices 1000 interconnected by a network. As can be appreciated, the network may be any suitable network, and each computing device 1000 may be connected thereto by communication connection(s) 1012 in any suitable manner, and each computing device 1000 may communicate with one or more of the other computing devices 1000 in the network in any suitable manner. For example, the network may be a wired or wireless network, such as within an organization or home, and may include a direct or indirect coupling to an external network, such as the Internet. Additionally, PCI, PCIe, and other bus protocols may be utilized to embed the various implementations described herein into other computing systems.

[0113] Interpretation of the disclosure herein It should be understood that the various techniques described herein may be implemented in connection with hardware or software or, where appropriate, with a combination of both. Thus, the processes and apparatus of the subject matter of this disclosure, or certain aspects or portions thereof, may take the form of program code (i.e., instructions) embodied in a tangible medium such as a floppy disk, a CD-ROM, a hard drive, or any other machine-readable storage medium that, when loaded into and executed by a machine, such as a computer, causes the machine to become an apparatus for practicing the subject matter of this disclosure.

[0114] When program code is executed on a programmable computer, the computing device generally includes a processor, a processor-readable storage medium (including volatile and non-volatile memory and / or storage elements), at least one input device, and at least one output device. One or more programs can perform or utilize the processes described in connection with the disclosed subject matter, for example, through the use of APIs, reusable controls, etc. Such programs can be implemented in a high-level procedural or object-oriented programming language to communicate with a computer system. However, the program(s) can also be implemented in assembly or machine language. In either case, the language may be a compiled or interpreted language, and may be combined with hardware implementations.

[0115] Although example implementations may refer to utilizing aspects of the presently disclosed subject matter in the context of one or more stand-alone computer systems, the subject matter is not so limited and may rather be implemented in connection with any computing environment, such as a network or distributed computing environment. Furthermore, aspects of the presently disclosed subject matter may be implemented within or across multiple processing chips or devices, and storage may similarly be affected across multiple devices. Such devices may include, for example, PCs, network servers, and handheld devices.

[0116] Certain implementations described herein may utilize a cloud operating environment that supports the provision of computation, processing, storage, data management, applications, and other functionality as abstract services rather than as standalone products such as computer hardware and software. Services may be provided by virtual servers, which may be implemented as one or more processes on one or more computing devices. In some implementations, processes may migrate between servers without interrupting the cloud service. In the cloud, shared resources (e.g., computation, storage) may be provided to computers, including servers, clients, and mobile devices, over a network. Different networks (e.g., Ethernet, Wi-Fi, 802.x, cellular) may be used to access cloud services. Users interacting with the cloud may not need to know details (e.g., location, name, server, database, etc.) of the devices actually providing the services (e.g., computation, storage). Users may access cloud services, for example, via a web browser, thin client, mobile application, or in other ways. To the extent any physical components of hardware and software are described herein, equivalent functionality provided via a cloud operating environment is also contemplated and disclosed.

[0117] Additionally, the controller service may reside in the cloud and may rely on a server or service for processing and a data store or database for storing data. While a single server, a single service, a single data store, and a single database may be utilized, multiple instances of servers, services, data stores, and databases may instead reside in the cloud and thus be used by the controller service. Similarly, a variety of devices may access the controller service in the cloud, and such devices may include (but are not limited to) computers, tablets, laptop computers, desktop monitors, televisions, personal digital assistants, and mobile devices (e.g., cell phones, satellite phones, etc.). It is possible that different users in different locations using different devices may access the controller service through different networks or interfaces. In one example, the controller service may be accessed by a mobile device. In another example, portions of the controller service may reside on the mobile device. Nevertheless, the controller service may perform operations including, for example, presenting content on a secondary display, presenting an application (e.g., a browser) on a secondary display, presenting a cursor on a secondary display, presenting controls on a secondary display, and / or generating control events in response to interactions on the mobile device or other services. In certain implementations, a controller service may perform portions of the methods described herein.

[0118] Possible alternatives Although the present subject matter has been described in language specific to structural features and / or methodological acts, it should be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features and acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the claims. Moreover, it will be apparent to one skilled in the art that other embodiments may be practiced apart from the specific details disclosed above.

[0119] The above drawings and the following written description of specific structures and functions are not presented to limit the scope of the invention or the appended claims. Rather, the drawings and written description are provided to teach one of ordinary skill in the art to make and use the invention for which patent protection is sought. Those skilled in the art will understand that, for the sake of clarity and understanding, not all features of a commercial embodiment of the invention are necessarily described or shown. Those skilled in the art will further appreciate that the block diagrams herein may represent conceptual views of illustrative circuitry embodying principles of the technology, and that any flowcharts, state diagrams, pseudocode, etc. represent various processes embodied in computer-readable media and therefore executable by a computer or processor, whether or not such a computer or processor is explicitly shown. The functionality of the various elements comprising the functional blocks can be provided through the use of dedicated electronic hardware as well as electronic circuitry capable of executing computer program instructions in association with appropriate software. Those skilled in the art will also appreciate that developing an actual commercial embodiment incorporating aspects of the present invention will require numerous implementation-specific decisions to achieve the developer's ultimate goals for the commercial embodiment. Such implementation-specific decisions may include, but are not limited to, compliance with system-related, business-related, government-related, and other constraints, which may vary by particular implementation, location, and may change over time. While a developer's effort may be complex and time-consuming in absolute terms, such an effort would nevertheless be a routine undertaking for one of ordinary skill in the art having the benefit of this disclosure.

[0120] It should be understood that the embodiments disclosed and taught herein are susceptible to numerous and various modifications and alternative forms. Accordingly, the use of singular terms such as "a" is not intended to limit the number of an item. Also, without limitation, the use of relational terms such as "top," "bottom," "left," "right," "upper," "lower," "below," "upper," "side," and the like are used in the written specification for clarity with specific reference to the figures and are not intended to further limit the scope of the invention or the appended claims. For particular embodiments described with reference to block diagrams and / or operational diagrams of methods, it should be understood that each block of the block diagrams and / or operational diagrams, and combinations of blocks in the block diagrams and / or operational diagrams, can be implemented by analog and / or digital hardware and / or computer program instructions. Computer program instructions for use in conjunction with or with the embodiments disclosed herein can be written in an object-oriented programming language, a conventional procedural programming language, or a lower-level code such as assembly language and / or microcode. The program may be executed entirely on a single processor and / or across multiple processors, either as a stand-alone software package or as part of another software package. Such computer program instructions may be provided to processors of a general-purpose computer, a special-purpose computer, an ASIC, and / or other programmable data processing system. The executed instructions may also create structures and functions for implementing the operations specified in the referenced block diagrams and / or operational diagrams. In some alternative implementations, the functions / operations / structures depicted in the figures may occur out of the order depicted in the block diagrams and / or operational diagrams. For example, two operations shown as occurring in succession may, in fact, be executed substantially simultaneously, or the operations may be executed in the reverse order, depending on the functions / acts / structures involved.

[0121] The term "computer-readable instructions," as used above, refers to any instructions that can be executed by a processor and / or other components. Similarly, the term "computer-readable medium" refers to any storage medium that can be used to store computer-readable instructions. Such media may take many forms, including, but not limited to, non-volatile media, volatile media, and transmission media. Non-volatile media may include, for example, optical or magnetic disks, such as storage devices. Volatile media may include dynamic memory, such as main memory. Transmission media may include coaxial cables, copper wire, and fiber optics, including the wires of a bus. Transmission media may also take the form of acoustic or light waves, such as those generated during radio frequency (RF) and infrared (IR) data communications. Common forms of computer-readable media may include, for example, a floppy disk, a flexible disk, a hard disk, magnetic tape, any other magnetic medium, a CD-ROM, a DVD, any other optical medium, punch cards, paper tape, any other physical medium with a pattern of holes, a RAM, a PROM, an EPROM, a FLASH-EPROM, any other memory chip or cartridge, a carrier wave, or any other medium from which a computer can read.

[0122] In the foregoing description, for purposes of explanation and not limitation, specific details are set forth, such as particular nodes, functional entities, techniques, protocols, standards, etc., to provide an understanding of the described technology. In other instances, detailed descriptions of well-known methods, devices, techniques, etc. are omitted so as not to obscure the description with unnecessary detail. All statements reciting principles, aspects, embodiments, and implementations, as well as specific examples, are intended to encompass both structural and functional equivalents, including both currently known equivalents and equivalents developed in the future, i.e., any elements developed that achieve the same functionality, regardless of structure. While the disclosed embodiments have been described with reference to one or more specific embodiments, those skilled in the art will recognize that many modifications thereto can be made. Accordingly, each of the foregoing embodiments and obvious variations thereof is contemplated as being within the spirit and scope of the disclosed embodiments, as set forth in the claims set forth below.

[0123] Copyright Notice A portion of the disclosure of this patent document contains material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as that material appears in the U.S. Patent and Trademark Office patent file or records, but otherwise reserves all copyright rights whatsoever. [Left blank]

Claims

1. 1. A method 700 for the separation of lead paste adhering to a lead alloy, comprising: mixing 702 the lead paste and lead alloy with a solution to form a mixture; agitating the mixture in a manner sufficient that the lead paste no longer physically adheres to the lead alloy 706-712; and removing 714 the lead alloy from the mixture.

2. The method of claim 1, wherein said agitating comprises rotary hammering of said mixture.

3. The method of claim 2 , wherein the rotary hammering is accomplished at least in part through the use of a rotating drum.

4. The method of claim 3 , wherein the rotating drum (722) comprises an internal baffle (726) that at least partially contributes to the rotary hammering (706).

5. 5. The method of claim 4, wherein the rotational speed of the rotating drum is maintained within a range that is substantially optimal for achieving the rotary hammering of the mixture.

6. 6. The method of claim 5, wherein the range is the rotational speed at which portions of the mass within the drum 722 are lifted above the central axis of the drum 722 and then fall below the central axis.

7. 10. The method of claim 1, wherein the mixture further comprises a cloth adhering to the lead paste, and wherein the agitating 706-712 causes the cloth to no longer adhere to the lead paste or the lead alloy.

8. 10. The method of claim 1, wherein the agitating includes vibrating a container in which the mixture is housed, the vibration being sufficient to cause mass transfer within the mixture.

9. 10. The method of claim 8, wherein the container includes a sieve through which the solution and the lead paste can pass but not the lead alloy.

10. 10. The method of claim 9, wherein the vibrating 712 the container 742 at least partially facilitates passage of the solution and the lead paste through the sieve 746.

11. 10. The method of claim 1, further comprising pressing 714 the lead alloy into a pressed form.

12. The method of claim 1 , wherein the solution 702 includes at least one auxiliary chemical that at least partially reduces adhesion of the lead paste to the lead alloy.

13. 1. A system 700′ for separation of lead paste adhering to a lead alloy, said system comprising at least one subsystem, said at least one subsystem comprising: rotary hammering 706 the mixture including the lead paste, the lead alloy, and a solution, wherein the rotary hammering 706 is performed in a manner sufficient such that the lead paste is no longer physically attached to the lead alloy; and separating 714 the lead alloy from the mixture.

14. 14. The system of claim 13, further comprising at least one subsystem whereby the rotary hammering is accomplished at least in part through the use of a rotating drum comprising an internal baffle that contributes at least in part to the rotary hammering by lifting portions of a mass within the drum above a central axis of the drum and then dropping the portions down the central axis.

15. 1. An apparatus 700' for the separation of lead paste adhering to a lead alloy, comprising: a rotating drum 722 for rotating and hammering 706 the mixture 702 including the lead paste, the lead alloy, and a solution, the rotary hammering 706 being performed in a manner sufficient such that the lead paste no longer physically adheres to the lead alloy; a vessel 740 for receiving the mixture from the drum and vibrating 712 the mixture sufficiently to cause mass transfer within the mixture and facilitate separation of the lead alloy from the lead paste and the solution; The apparatus 700' comprises a press 728' for pressing 714 the lead alloy into a pressed form.

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