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    • 专利摘要:
    systems and methods for continuous recycling of the alkaline lead-acid battery. The present invention relates to lead that is recycled from the lead slurry of lead-acid batteries in a process employing alkaline desulfurization followed by formation of plumbite which is then electrolytically converted to pure lead. the remaining insoluble lead dioxide is removed from the lead plumbite solution and reduced to produce lead oxide which can be fed back into the recovery system. the sulfate is recovered as sodium sulfate, while the lead oxide produced in this way can be added to lead slurry for recovery.
    公开号:BR112018011217B1
    申请号:R112018011217-8
    申请日:2016-12-02
    公开日:2022-01-18
    发明作者:Robert Lewis Clarke；Samaresh Mohanta
    申请人:Aqua Metals Inc；
    IPC主号:
    专利说明:

    [001] This application claims priority from the US application under serial number 14/957,026, which was filed December 2, 2015. Field of Invention
    [002] The field of the invention is lead-acid battery recycling, especially in relation to alkaline aqueous recycling processes and the continuous recovery of pure lead using these processes. Background of the Invention
    [003] The description of the background includes information that may be useful in understanding the present invention. It does not assume that any information provided herein constitutes prior art or is relevant to the invention claimed herein or that any publication specifically or implicitly cited constitutes prior art.
    [004] Although lead from lead-acid batteries is almost entirely recycled, most known processes are environmentally and economically problematic. For example, when lead is recycled using smelting operations, air and water pollution, along with the production of substantial amounts of toxic waste, has caused many recycling plants to close. Additionally, in order to meet stringent demands on emissions and energy efficiency, recycling of lead-acid batteries has forced increased throughput from operations, which causes logistical challenges.
    [005] To help overcome some of the difficulties with smelting operations, various systems and methods for lead-free lead recovery have been developed. For example, US 4,460,442 teaches a lead recovery process in which lead and lead dioxide are rectified and reacted with a strong alkaline solution to produce solid ominium (Pb3O4) which is then subjected to further reaction with acid. fluorosilic acid or fluoroboric acid to dissolve the lead, which is then electroplated from these acids onto a graphite anode. Similarly, U.S. 4,769,116 teaches carbonation reactions of lead paste and subsequent reaction with fluorosilic or fluoroboric acid to form an electrolyte from which the lead is plated. All publications and patent applications noted herein are incorporated by reference in the same manner as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. When a definition or use of a term in an incorporated reference is inconsistent with or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply. While such a process advantageously avoids casting, however, several difficulties remain. Most notably, digestion with fluorosilic or fluoroboric acid is undesirable in the environment and waste materials contain substantial amounts of lead sulfate.
    [006] Lead paste can also be desulfurized using caustic soda (NaOH) or sodium carbonate (Na2CO3) to produce the corresponding lead hydroxides or lead carbonates from lead sulfate. Alternatively, amine solvents can be used in desulfurized lead slurry and produce purified lead sulfate and recycled amine solvent as described elsewhere (Journal of Achievements in Materials and Manufacturing Engineering 2012, Volume 55(2), pages 855 to 859). Unfortunately, such a process allows the production of pure elemental lead.
    [007] Desulfurization can be followed by treating lead oxides with an acid and a reducing agent to form a lead salt which is then reacted with a second base under a CO2 free atmosphere at an elevated temperature to form PbO as per described in WO 2015/057189 . Although such a process allows for the production of PbO, multiple solvent and reagent treatment steps are required, and pure elemental lead is not readily obtained from such a process. Similarly, US 2010/043600 discloses a process for recovering high purity lead compounds from pulp in which lead oxide is first dissolved in an acid, in which insoluble lead dioxide is reduced, and in which the lead oxide thus obtained is converted to lead sulfate which can then be converted to the corresponding carbonate, oxide, or hydroxide. Unfortunately, such a process is relatively complex and is thus typically and economically unattractive.
    [008] In yet another example, WO 2015/084950 describes a process in which lead slurry from a battery is first reacted with nitric acid to convert lead dioxide to lead nitrate and in which lead sulfate lead is recovered from the solution using sulfuric acid to regenerate nitric acid. Lead sulphate from battery paste is subjected to alkali to precipitate lead oxides which are then, after sulphate removal, converted to lead carboxylate as a raw material for lead monoxide. Unfortunately, the processes described in the '950 application are complex and may not always result in complete recycling and production of pure lead. Significant improvements have been revealed in the document in WO 2015/077227 where the lead paste from lead-acid batteries is dissolved in a solvent system that allows the digestion of both lead oxide and lead sulfate, and from which lead elemental can be electrolytically deposited in a chemically pure form. While such a system advantageously allows high recovery of lead in a conceptually simple and effective manner, sulfate accumulation in the electrolyte will nevertheless require solvent treatment.
    [009] Thus, although there are numerous systems and methods for recycling lead known in the art, there is still a need for improved systems and methods that produce high purity lead in a simple and cost-effective manner. Summary of the Invention
    [010] The inventive matter is directed to various improved lead-acid battery recycling systems and methods in which lead from the active materials in the lead slurry is subjected to an alkaline process that allows for simple sulfate removal while also allowing for recovery. lead electrolyte in pure form.
    [011] In one aspect of the inventive matter, the method of recovering lead from a battery slurry that includes lead oxides and lead sulfate comprises a step of bringing the battery slurry into contact with an aqueous base (e.g. NaOH or Na2CO3) to form a precipitate containing lead hydroxide and sodium sulfate solution. The lead hydroxide-containing precipitate is then separated from the sodium sulfate solution, and at least a portion of the lead hydroxide-containing precipitate is dissolved in a concentrated aqueous base to yield an electrolyte containing lead and insoluble lead dioxide. In yet another step, adhering lead is continuously formed and removed at an electrode that comes into contact with the lead-containing electrolyte.
    [012] More typically, the aqueous base is added in an amount sufficient to produce lead hydroxide from lead oxide without substantial production of plumbite (e.g., equal to or less than 5 mol%, and more typically equal to or less than that 2 mol% of all lead species are converted to plumbite). Contemplated methods will additionally include a step of separating the insoluble lead dioxide from the lead-containing electrolyte, and another step of reducing the lead dioxide to lead oxide. Most preferably, the reduction of lead dioxide is carried out using sodium sulfide to produce sodium sulfate and lead oxide. In such a case, the sodium sulfate so produced and the sodium sulfate solution are electrolyzed to produce sodium hydroxide and sulfuric acid, and the lead oxide is combined with the aqueous base. Consequently, all reagents can be fully recycled.
    [013] In general, it is additionally preferred that the precipitate containing lead hydroxide is dissolved in the concentrated aqueous base to convert substantially all of the lead hydroxide to plumbite, and/or that the step of continuously forming and removing adhering lead is carried out with the use of a moving electrode (for example, a rotating electrode, a belt electrode, or an alternating electrode). Suitable electrode materials include various caustic inert metals and alloys, however, especially preferred electrodes will comprise nickel plated steel. Where the electrode is a moving electrode, it is generally contemplated that the adherent lead formed on the moving electrode has an apparent density of less than 11 g/cm3 and has a purity of at least 99% atomic.
    [014] Therefore, and viewed from a different perspective, the inventors also contemplate a method of recovering lead from a battery slurry comprising lead oxides and lead sulfate that includes a step of bringing the battery slurry into contact with a aqueous base to form a precipitate containing lead and a solution of sodium sulfate. In another step, the lead-containing precipitate is separated from the sodium sulfate solution, and at least a portion of the lead-containing precipitate is dissolved in an electrolyte fluid to yield an electrolyte containing lead and insoluble lead dioxide. In an additional step, the insoluble lead dioxide and sodium sulfate solution are processed to generate components suitable for use in the step of bringing the battery paste into contact with the aqueous base, while, in an even further step, the lead Adhesive is continuously formed and removed at an electrode that comes into contact with lead-containing electrolytes.
    [015] It is generally contemplated that the aqueous base is added in an amount sufficient to produce lead carbonate or lead hydroxide from lead oxide. Thus, suitable electrolyte fluids especially include sodium hydroxide solutions, sodium carbonate solutions, and metasulfonic acid solutions. Accordingly, the lead-containing precipitate may comprise lead hydroxide or lead carbonate, and may additionally comprise lead dioxide.
    [016] In even more contemplated aspects, insoluble lead dioxide can be separated from lead-containing electrolyte and subjected to a chemical reaction to reduce lead dioxide to lead oxide (e.g. by converting insoluble lead dioxide into lead oxide with the use of sodium sulfide and by converting the sodium sulfate solution to a sodium hydroxide solution). Alternatively it is also contemplated that other reducing agents such as hydrogen peroxide, hydrazine sulfate or sodium dithionate can be used to reduce lead dioxide to lead oxide.
    [017] Where the electrolyte fluid is metasulfonic acid solution, especially preferred electrodes comprise aluminum, while the electrode in alkaline electrolytes is preferably nickel-plated steel. Depending on the particular solvent, it is contemplated that at least a portion of the lead-containing electrolyte after the continuously forming and removing step is treated to reduce a sodium ion concentration (e.g., by precipitation with strong HCl such as NaCl, by means of reverse osmosis, electrodialysis, or other suitable method).
    [018] Various objects, features, aspects and advantages of the subject matter of the invention will become more evident from the following detailed description of the preferred embodiments, together with the accompanying figures in which like numerals represent like components. BRIEF DESCRIPTION OF THE FIGURES
    [019] Figure 1 is a first exemplary process according to the inventive matter.
    [020] Figure 2 is a second exemplary process according to the inventive matter.
    [021] Figure 3 is a third exemplary process according to the inventive matter.
    [022] Figure 4 is an example graph showing comparative desulfurization results. Detailed Description
    [023] The inventors have now found that lead from lead slurry can be electrolytically recovered in a conceptually simple and effective way using an alkaline desulfurization process in which lead oxide and lead sulfate from the slurry are reacted with a base to convert the lead species into the corresponding insoluble lead salts which form a precipitate and to produce a sulfate solution which is then separated from the precipitate. The precipitate (e.g. typically lead hydroxide or lead carbonate) and the remaining insoluble lead oxides (e.g. lead dioxide) are then subjected to a substantially higher pH, yielding soluble plumbite (e.g. Na2PbO2) and undissolved lead dioxide that is removed from the plumbite solution. Undissolved lead dioxide is reduced to lead oxide (e.g. using sodium sulfide or hydrogen peroxide) and recycled for further processing, and pure lead is recovered from the plumbite solution on a moving electrode to produce adherent lead. Alternatively, the precipitate can be dissolved in an electrochemically stable acid (eg metasulfonic acid) and recovered as pure lead, while the remaining undissolved lead dioxide is recycled as noted above.
    [024] In an especially preferred aspect, lead-acid batteries are disintegrated and metallic lead, plastic and sulfuric acid are collected as is known in the art. The remaining active material slurry comprising lead oxides and lead sulfate (e.g. 12 to 16 mol % PbO, 18 to 25 mol % PbO2, 54 to 60 mol % PbSO4, 1 to 3 % in mol of Pb) is collected and rinsed as appropriate or required (eg with the use of water, base or sulfuric acid). Plastic, metallic lead, and sulfuric acid can be processed in a number of ways. For example, polymeric materials can be recycled to form new battery components or other valuable products, while metallic lead (e.g. grid lead) can be cleaned and pressed into lead chips or ingots to then yield recycled grid lead that it can be directly reused or further refined in a downstream process as needed. Similarly, the recovered sulfuric acid can be used in the manufacture of new lead-acid batteries, typically after a filtration or other cleaning process.
    [025] The active material slurry is then subjected to a desulfurization step in which soluble sulfate salts of the base (typically sodium sulfate) are formed in a typically dilute aqueous solution and at a pH that is suitable to promote formation of insoluble lead hydroxide from lead sulfate and lead oxide without substantial production of lead (e.g., equal to or less than 5 mol%, more typically, equal to or less than 1 mol%, even more typically , equal to or less than 0.1 mol%, and most typically, equal to or less than 0.01 mol% of all lead species are converted to plumbite). More typically, desulfurization is carried out using sodium hydroxide in water at concentrations of between about 2.0M to 4.0M, at a temperature of between about 20°C to 50°C, and for a period from about 10 min to 60 min, or 1 to 2 hours, or 2 to 6 hours, or 6 to 12 hours, or even longer. Unless the context states otherwise, all ranges presented in this document should be interpreted as being inclusive of their endpoints and open ranges should be interpreted as including commercially practical values. Similarly, all lists of values should be considered to be inclusive of intermediate values unless the context dictates otherwise. However, it should be noted that several other process conditions are also considered suitable and include lower molarities of sodium hydroxide, including 1.0M to 2.0M, or 0.1M to 1.0M. similarly, higher molarities of sodium hydroxide, including 4.0M to 6.0M, or 6.0M to 8.0M are also contemplated, typically with shorter reaction times and/or lower temperatures. Thus, the pH of the desulfurization reaction is typically between 8.0 and 9.0, between 9.0 and 10.0, or between 10.0 and 11.0. Similarly, it should be noted that the temperature of the desulfurization reaction will be between about 10°C to 30°C, or between about 20°C to 50°C, or between about 50°C to 70°C. , and in some cases even higher.
    [026] In further contemplated aspects of the inventive matter, it should be noted that the base solution need not be limited to sodium hydroxide, but may also include various other hydroxides and/or carbonates (e.g. KOH, Na2CO3, etc. .) in amounts and at a pH suitable for dissolving lead sulfate in the corresponding soluble lead salt. As noted above, it will generally be preferred that the base solution be used in an amount sufficient to produce lead hydroxide or carbonate (or other species) of lead sulfate and lead oxide without substantial production of plumbite. Viewed from another perspective, the resulting aqueous solutions will contain significant amounts of precipitate which contain lead hydroxide or carbonate and dissolved sodium sulfate. Since lead dioxide is generally insoluble (or only minimally soluble) in aqueous alkaline solutions, the precipitate will also include verifiable amounts of lead dioxide (and to some degree, elemental lead as well). Thus, desulfurization of lead paste from lead-acid batteries will result in a precipitate that contains lead hydroxide or lead carbonate that additionally includes insoluble lead dioxide and elemental lead.
    [027] Advantageously, the sulfate-rich solution generated in this way is separated from the precipitate and further processed. Especially preferred processing steps include electrolytic treatment wherein the sulfate-rich solution is an aqueous solution of sodium sulfate. Sodium sulfate electrolysis will yield sodium hydroxide and sulfuric acid, both of which can be recycled. For example, sodium hydroxide can be used as the base for desulfurization and as the electrolyte in the lead recovery process, while sulfuric acid can be used as battery acid in newly produced batteries. Alternative uses of sulfate alone include precipitation with calcium ions to produce gypsum as a valuable product or precipitation with ammonium ions to yield ammonium sulfate. Additionally, it should be noted that sodium sulfate can also be (continuously) removed from the electrolyte by cooling at least a portion (e.g. mat) of the electrolyte to a temperature low enough to crystallize sodium sulfate, which can then be removed from the electrolyte.
    [028] Where desired, the precipitate can be washed using various solutions to reduce residual sulfate. More typically, such a wash solution is an aqueous solution and may include dilute base (e.g., sodium hydroxide solution), water, or other fluid which may preferably be recycled into the process. Residual sulfate in the precipitate is preferably present in concentrations at or below 2 mol%, more typically at or below 1 mol%, even more typically at or below 0.1 mol%, and most typically at or below below 0.01% by mol. However, it should be noted that where the precipitate is subsequently dissolved in an acid (e.g. methane sulfonic acid), residual sulfate is less crucial, but residual sodium will preferably be present at concentrations at or below 2 mol %, more typically at or below 1 mol %, even more typically at or below 0.1 mol %, and most typically at or below 0.01 mol %.
    [029] Regardless of the way the precipitate is treated, it should be verified that the remaining lead species include lead hydroxide, lead dioxide and metallic lead. Although the lead hydroxide or lead carbonate in the precipitate can be readily dissolved in various solvents as is further discussed in more detail below, it should be recognized that lead dioxide and metallic lead are not readily soluble in most solvents. However, lead dioxide does not represent a significant portion of the lead slurry in recycled batteries (typically at least 5% by mole, more typically at least 10% by mole, and most typically at least 15% by mole), and would be lost to the recovery process if not further treated. Advantageously, lead dioxide can be reduced to lead oxide as is further described in more detail below, and the lead oxide generated in this way can then reenter the recovery process (typically by adding lead or aqueous base to the slurry) .
    [030] In a still further aspect of the invention, the precipitate is combined with a preferably aqueous electrolyte fluid that dissolves lead hydroxide and/or lead carbonate to thereby yield an electrolyte containing lead and insoluble lead dioxide. . While not limiting the inventive subject matter, especially preferred electrolyte fluids include methane sulfonic acid and sodium hydroxide in a relatively high concentration. Although methane sulfonic acid (MSA) is employed to at least partially dissolve lead-containing precipitate, it is contemplated that the electrolyte may also include a lead ion chelating agent, and especially EDTA (ethylenediaminetetraacetic acid). On the other hand, where the electrolyte is an aqueous sodium hydroxide solution, it will generally be preferred that such a solution will have a concentration and pH effective to convert substantially all (e.g., at least 95% by mol, more typically at least 98% in mol, most typically at least 99% by mol) lead hydroxide in plumbite which is highly soluble in aqueous base solutions. As a result, it should be recognized that the electrolyte will now contain dissolved ionic lead species while other heavy metals that are potentially present in the battery and electrolyte paste (e.g. Sb, Ca, Sn, Cu, As) will not be dissolved in the electrolyte. and thereby will not adversely interfere and/or plaque the subsequent electrolytic recovery of lead as further described in more detail below.
    [031] Undissolved lead dioxide can be readily isolated from lead-containing electrolytes through filtration, sedimentation, centrifugation, etc., and is preferably further processed in a reduction process in which lead dioxide is converted to lead oxide. lead. Most preferably, the reducing agent is compatible with the recovery systems and methods described herein, including various organic acids (e.g., oxalate), hydrogen peroxide, hydrazine sulfate, and sodium sulfide. For example, when the reducing agent is sodium sulfite, the reduction reaction will yield lead oxide and sodium sulfate. Sodium sulfate thus generated can be combined with sodium sulfate obtained from the desulfurization reaction for recycling in the process, while lead oxide can be combined with battery paste 109 or aqueous base to form more lead hydroxide in the process. process.
    [032] Of course, it should be noted that the lead dioxide present in the battery paste 109 can also be reduced prior to desulfurization to form a pre-treated battery paste that has a significantly reduced concentration of lead dioxide (e.g., lead dioxide of residual lead equal to or less than 5% by mol, or equal to or less than 2% by mol, or equal to or less than 0.5% by mol, or equal to or less than 0.1% by mol of all species of lead in the pre-treated paste). Pretreatment is typically performed using a reducing agent which is suitable for forming lead oxide from lead dioxide, and especially suitable reducing agents include hydrogen peroxide, sulfur dioxide gas (fed to an aqueous solution) , hydrazine sulfate and sodium sulfide. For example, hydrogen peroxide will reduce lead dioxide and yield lead oxide and water, and when the reducing agent is sodium sulfite, the reduction reaction will yield lead oxide and sodium sulfate. As noted earlier, the battery slurry pretreated in this way can then be subjected to the desulfurization reaction. Alternatively, lead dioxide can also be reduced to an acid electrolyte with the use of peroxide or other time reducing agent when desulfurized lead precipitates are dissolved in the electrolyte acid.
    [033] Regarding lead-containing electrolytes, it will generally be preferred that the electrolyte be subjected to electrolytic recovery of lead, preferably with the use of a continuously moving electrode in order to form adherent lead. As used herein, the term "sticky", when used in conjunction with metallic lead formed through ionic lead reduction refers to a form of lead that is not a consistent film bonded to a cathode surface, but which is amorphous and can be cleaned from the cathode. In other words, an adherent lead product does not form, in a macroscopic dimension, intermetallic bonds between the cathode and the lead product and therefore will not form a consistent lead film on the cathode. For example, through observation in most experiments, lead formed in a low density micro or nanocrystalline layer that was loosely attached to the cathode, floated from a static plate cathode, and could be washed off the surface of a rotating cathode if the electrolyte circulation was too aggressive. The formation of adherent lead on the electrode is particularly advantageous where the electrode comprises a moving surface. In most cases the inventors have found that less than 10% (e.g. between 5 to 9%), more typically less than 7% (e.g. between 2 to 6%), even more typically less than 5% (e.g., between 1 to 4%), and more typically, less than 3% (e.g., between 0.01 to 2%) of the total lead formed at the cathode was found to be plated and strongly bound lead at the cathode, while the remainder of the lead remained in the form of low adhering density. Among other advantages, and while not limited to any theory or hypothesis, the inventors contemplate that the relative movement of electrolyte and electrode will result in micro or nanocrystalline growth of elemental lead on the electrode surface, which, in turn, appears to promote formation and/or capture of hydrogen. Notably, hydrogen associated with sticky lead will have at least two desirable effects with respect to lead chemistry: First, lead is sticky and easily removed from the electrode surface which is commonly not achieved with static electrodes and alternative lead salts. Second, the adhering lead produced in this way has micro- or nanocrystalline growth structures with relatively large surface area that are protected from oxidation (or passivation) by the hydrogen-reducing microatmosphere in the adhering lead. Consequently, the adherent lead produced in this way is readily cold conformable by compression to larger macroscopic structures without formation of grain boundaries. Particular devices and methods suitable for producing adherent lead are disclosed in commonly owned WO 2015/077227, which is incorporated by reference herein.
    [034] A first exemplifying process according to the inventive matter is shown in Figure 1 where the battery recycling process employs an upstream desulfurization process in which the lead slurry (comprising lead sulfate and lead oxides) is combined with sodium carbonate and hydrogen peroxide. As noted earlier, lead sulphate from battery paste is converted to lead carbonate and highly soluble sodium sulphate is formed which can be readily removed from the precipitated lead carbonate. To reduce the sodium-lead carbonate concentration, the pH of the desulfurization mixture can be reduced to about pH 6.0 (eg with the use of sulfuric acid). At this stage, the lead dioxide is reduced to lead oxide by means of hydrogen peroxide, and it should be verified that the lead dioxide can be derived from the paste alone or in combination with lead dioxide from the later dissolving step. lead carbonate/oxide in the electrolyte. Once the desulfurization reaction has completed or reached an acceptable degree of desulfurization (e.g. at least 90%, or at least 95%, or at least 99% of all lead sulfate converted to lead carbonate), the carbonate of lead and lead oxide are processed to remove the desulfurization solution. Of course, it should be verified that a rinsing step (eg with water or electrolyte) can be implemented prior to processing. More typically, processing is carried out by filter pressing, but other ways of processing are also contemplated, including heating, centrifuging, etc. The desulfurization solution can then be subjected to one or more sulfur recovery steps (e.g. precipitation with suitable cations or via sodium sulfate crystallization at a reduced temperature (e.g. between 15 to 25 °C, or between 10 to 15 °C, or between 5 to 15 °C, or between 0 to 15 °C, etc.), or through ion exchange or reverse osmosis, etc.), while recovered water can be processed or fed at a waste water treatment plant.
    [035] The lead carbonate/lead oxide obtained in this way (possibly with smaller amounts of lead dioxide) is then dissolved in an acid electrolyte which is stable under electroplating conditions and dissolves lead at high concentrations. Most preferably, such an electrolyte is methane sulfonic acid as discussed above, and alternative electrolytes include halogenated alkane sulfonic acids, etc. Once the process of dissolving the lead carbonate/lead oxide in the acid electrolyte is complete, any remaining undissolved lead species (and especially remaining lead dioxide) is removed in a separator and optionally fed back to the desulfurization while dissolved lead species are fed to an electrolyte feed tank. Elemental lead is (preferably and continuously) removed as lead adhering to the electrode as further discussed below while the depleted electrolyte is recycled back to dissolve new carbonate/lead oxide.
    [036] Alternatively, the desulfurization step could also be performed using sodium hydroxide instead of sodium carbonate as shown in the second exemplifying process in Figure 2. Here, the battery recycling process employs a desulfurization process upstream in which lead slurry (comprising lead sulfate and lead oxides) is combined with sodium hydroxide and hydrogen peroxide. As noted earlier, lead sulphate from battery paste is converted to lead hydroxide and highly soluble sodium sulphate is formed which can be readily removed from the lead hydroxide precipitate. To reduce the concentration of lead dissolved in the sodium sulfate solution in such a process, the pH of the desulfurization mixture can be raised to about pH 9.0 (eg with the use of sodium hydroxide). As noted above, lead dioxide is reduced to lead oxide by means of hydrogen peroxide, and it should be noted that lead dioxide can be derived from the slurry alone or in combination with lead dioxide from the step later to dissolve lead hydroxide/oxide in the electrolyte. Once the desulfurization reaction has completed or reached an acceptable degree of desulfurization (e.g. at least 90%, or at least 95%, or at least 99% of all lead sulfate converted to lead hydroxide), the hydroxide of lead and remaining lead oxide are processed to remove the desulfurization solution. Of course, it should be verified that a rinsing step (eg with water or electrolyte) can be implemented prior to processing. More typically, processing is carried out by filter pressing, but other ways of processing are also contemplated, including heating, centrifuging, etc. The desulfurization solution can then be subjected to one or more sulfur recovery steps (e.g. precipitation with suitable cations or via sodium sulfate crystallization via ion exchange or reverse osmosis, etc.) can be processed or fed to a waste water treatment plant.
    [037] The lead hydroxide/lead oxide obtained in this way (possibly with smaller amounts of lead dioxide) is then dissolved as above in an acid electrolyte which is stable under electroplating conditions and dissolves lead in high concentrations. Most preferably, such an electrolyte is methane sulfonic acid as discussed above, and alternative electrolytes include halogenated alkane sulfonic acids, etc. Once the process of dissolving the lead hydroxide/lead oxide in the acid electrolyte is complete, any remaining undissolved lead species (and especially remaining lead dioxide) is removed in a separator and optionally fed back to the desulfurization while dissolved lead species is fed to an electrolyte feed tank. Elemental lead is again (preferably and continuously) removed as lead adhering to the electrode as discussed below while the depleted electrolyte is recycled back to dissolve new carbonate/lead oxide . Table 1 provides a comparison for various exemplary process parameters for the desulfurization options of Figures 1 and 2.

    Table 1
    [038] In yet another contemplated process as shown exemplifying in Figure 3, the lead paste comprising lead sulfate and lead oxides is, after a step of removing sulfuric acid or washing means (e.g., by means of a filter press), combined with sodium hydroxide under conditions effective to convert lead sulfate and lead oxide to the corresponding lead hydroxide precipitate while forming highly soluble sodium sulfate which can be readily removed from the lead hydroxide precipitate. Residual undissolved lead dioxide is then reduced (eg with sodium sulfide or other agent as discussed above) to lead oxide which will be readily converted to lead hydroxide. Additionally, as noted above, lead dioxide can also be reduced to lead oxide by means of hydrogen peroxide (or sulfite), and it should be noted that such a reduction can be carried out in the battery paste, or in a later step. to dissolve lead hydroxide/oxide in the electrolyte. Alternatively, non-desulfurized lead slurry can be employed as a starting material in such a process. In the example in Figure 3, non-desulfurized lead slurry is converted to lead plumbite (Na2Pb(OH)4) using sodium hydroxide to achieve a pH suitable for lead plumbite formation (e.g. pH > 11.5). Any undissolved material is then removed from the alkaline electrolyte in one or more separators and the alkaline electrolyte thus obtained is fed to an electrolyte feed tank. It should be noted that sulfate can be recovered from the electrolyte (preferably after electrolysis) using various methods, and suitable methods include cooling and precipitating sodium sulfate from at least a portion of the electrolyte, specific precipitation, electrodialysis, or ion exchange. Elemental lead is again (preferably and continuously) removed as lead adhering to the electrode as discussed below while the depleted electrolyte is recycled back to dissolve additional lead slurry.
    [039] For example, and generally following the process of Figure 3, the desulfurization and digestion of lead-acid battery paste by sodium hydroxide was performed in one step (here: no sodium sulfate removal between steps of sodium hydroxide precipitation and formation of plumbite, which can be readily implanted as discussed above). 100 g of used lead-acid battery paste was treated with 2 liters of solution containing 960 g of 50% commercial grade sodium hydroxide solution and deionized water. The reaction was carried out for one hour in a 4 liter beaker with baffles for better turbulence. Samples of the solution were then taken at 1, 5, 30 and 60 minutes reaction time. The samples were filtered, and the filtered samples were subsequently analyzed for dissolved lead concentration. The recovery of lead extraction in the solution was calculated by dividing the amount of original paste by the amount of lead dissolved in the solution. It should be noted that in such a process the sulfate produced remains in the alkaline electrolyte, and that the sulfate can be removed from the alkaline electrolyte using various methods, and suitable methods include cooling and precipitating sodium sulfate from at least one electrolyte portion, specific precipitation, electrodialysis, or ion exchange (eg, as shown in Figure 3).
    [040] Therefore, it should be noted that the inventors also contemplate a method of recovering lead from a battery slurry comprising lead oxides and lead sulfate. Such a method will typically include a step of contacting the battery paste with an aqueous base to form an alkaline electrolyte fluid that contains dissolved sodium sulfate and plumbite, an additional step of continuously forming and removing adhering lead from the plumbite at an electrode that is in contact with the alkaline electrolyte fluid, and yet another step of removing at least some of the sodium sulfate from the alkaline electrolyte fluid. Some such steps can be carried out following a process scheme substantially similar to that shown in Figure 3.
    [041] A comparative study was performed with a two-step desulfurization process using sodium hydroxide to form lead hydroxide precipitate, followed by methane sulfonic acid digestion as substantially shown in Figure 2. The extraction recovery lead was found to be 25.6% compared to 24.8% for the single step as shown as an example in Figure 4. As can be seen from the graph, the recovery difference is within the experimental error and is not significant.
    [042] To demonstrate the feasibility of digesting a NaOH-desulfurized battery slurry to thereby produce plumbite, the inventors combined in a 2,000 µl beaker, fitted with baffles and a stirrer, 498 g of deionized water and 101 g of battery slurry of used lead acid that was previously desulfurized using sodium carbonate (sodium carbonate). The stirrer was set to 600 rpm. 60 g of NaOH pellets were added to this mixture. The final weight of the slurry obtained after 150 minutes was 594 g. The slurry was filtered through a Buchner funnel to separate the solids from the liquid. The solids were washed with 68 g of deionized water. The filtrate contained 25.0 g/l of lead. Again, dissolved sulfate can be removed from the alkaline electrolyte using a variety of methods, and suitable methods include cooling and precipitating sodium sulfate from at least a portion of the electrolyte, specific precipitation, electrodialysis, or ion exchange (e.g. , as shown in Figure 3). Sulfate removal can be performed before or after lead plating of the alkaline electrolyte.
    [043] High purity lead plating of the plumbite solution was carried out as follows: 380 g of the filtrate was placed in the plating tank of a small scale Aqua Refining cell (see for example document no WO 2016/183429 ). The cell was fitted with a 4” diameter aluminum disc cathode, centrally located between two iridium oxide coated titanium blend anodes. The cathode was rotated at approximately 5 rpm, and a current of 2.12 A was applied for 1 hour, after which the lead concentration in the plating tank was 1.2 g/l. A lightweight low-density lead composition containing about 85% by weight of entrained electrolyte was collected on the cathode surface. Notably, this lead composition was deposited as adherent-forming lead, but without film. Furthermore, the bulk density of the lead composition was less than 11 g/cm3 , and more typically less than 9 g/cm3 , and most typically less than 7 g/cm3 . After deliquefaction, 8.5 g of wet lead (which typically has a purity of at least 98% by mole, or at least 99% by mole, or at least 99.9% by mole) was obtained. Faradaic efficiency was close to 100%.
    [044] While the absence of plating is typically undesired in all or nearly all electrodeposition methods, the inventors have now discovered that such absence of plating will enable a continuous lead recycling process in which lead can be continuously removed from the cathode in one segment while additional lead is formed on another segment of the cathode. Removal of adhering/weakly associated lead will typically be accomplished with the use of a mechanical implant (e.g. a cleaning surface, shovel or other tool close to the cathode, etc.), however, removal can also be accomplished through from non-mechanical tools (e.g. through electroprocessor solvent blasting against the cathode, or injection gas against the cathode, etc.). In addition, it should be noted that removal may not use an implantation, but be done merely by passively releasing the low-density lead material from the cathode and floating to the surface of the electrochemical cell (where an overflow spillway or stripper is used). will receive lead materials).
    [045] Viewed from a different perspective, it should also be recognized that a moving electrode for depositing adherent/micro or nanocrystalline lead would advantageously allow continuous lead recovery as opposed to static electrodes. Among other things, large electrolytic recovery operations for lead often encounter interruptions in the current supply. Since most static electrolyte recovery units typically operate with an acid electrolyte (eg, fluoroboric acid), plated lead will redissolve into electrolyte upon electrical potential collapse. Continuous recovery will not have such a defect as lead loss is limited to only a relatively small section of the moving electrode (ie the section that is in contact with the electrolyte). Most preferably, contemplated electrodes are shapes such as disc electrodes, cylinder electrodes, belt electrodes, or alternating electrodes, and lead is preferentially and continuously removed from the electrode surface using a cleaning implant proximal to the electrode surface. Once enough adherent lead has been deposited on the electrode surface, lead captures on the cleaning implant (e.g. polymer trough or light cleaning blade) and movement of the electrode past the cleaning implant causes the adherent lead to disengage. from the electrode and fall. Preferred electrode materials can vary considerably, however, particularly preferred electrode materials include electrodes of nickel plated steel, stainless steel, graphite, copper, titanium, manganese dioxide, and even conductive ceramics.
    [046] Most notably, and in relation to adherent lead, it should be noted that metallic lead was recovered from the processes of the inventive concept in the form of a micromatrix or mixed nanoporous matrix in which micro or micro-sized structures lead nanoforms (typically needles/wires) that captured some of the electroprocessor/electrodeposition solvent and a substantial amount of molecular hydrogen (ie H2). Most notably, such a matrix had a black appearance and a remarkably low bulk density. In fact, in most experimental tests the matrix was observed to float on top of the solvent and had a density of less than 1 g/cm3. Upon die pressure or application of another force (and still under the influence of its own weight), the gross density increased (e.g. 1 to 3 g/cm3, or 3 to 5 g/cm3, for that of lead ingot pure ) and a metallic silver glow appeared. Additionally, the recovered lead had a relatively high purity, and in most cases, the lead purity was at least 95 mol%, or at least 97 mol%, or at least 99 mol% of all metallic species. .
    [047] As used in the description herein and by all claims that follow, the meaning of "a", "an" and "the (a)" includes plural reference unless the context clearly indicates otherwise. In addition, as used in the description herein, the meaning of "in" includes "in" and "on", unless the context clearly indicates otherwise. As used herein, and unless the context dictates otherwise, the term "coupled to" is intended to include both direct coupling (where two elements that are coupled together come into contact) and indirect coupling (where at least one additional element is located between the two elements). Thus, the terms "coupled to" and "coupled with" are used synonymously. It should be noted by those skilled in the art that many further modifications than those already described are possible without departing from the inventive concepts herein. The inventive matter, therefore, should not be restricted, except within the scope of the appended claims. Furthermore, in interpreting both the specification and the claims, all terms should be interpreted as broadly as possible consistent with the context. In particular, the terms "comprises" and "comprising" should be interpreted when referring to elements, components or steps in a non-exclusive manner, which indicates that the mentioned elements, components or steps may be present, or used or combined. with other elements, components or steps that are not expressly mentioned. When the descriptive report claims refer to at least one of something selected from the group consisting of A, B, C... and N, the text should be interpreted as requiring only one element of the group, not A plus N, or B plus N, etc.
    权利要求:
    Claims (20)
    [0001]
    1. METHOD OF CONTINUOUS RECOVERY OF LEAD FROM A BATTERY PASTE COMPRISING LEAD OXIDES AND LEAD SULFATE characterized in that the steps of: bringing the battery paste into contact with an aqueous base to form a precipitate containing hydrogen hydroxide lead and a sodium sulfate solution; separating the lead hydroxide-containing precipitate from the sodium sulfate solution; dissolving at least a portion of the lead hydroxide-containing precipitate in a concentrated aqueous base that has a pH sufficient to form soluble plumbite to thereby yield a lead-containing electrolyte; and continuously forming and removing adhering lead at pH on a moving electrode that comes into contact with the lead-containing electrolyte, wherein the lead has a purity of at least 95% by mol.
    [0002]
    2. METHOD, according to claim 1, characterized in that the aqueous base is added in an amount sufficient to produce lead hydroxide from lead oxide without substantial production of plumbite.
    [0003]
    3. METHOD, according to claim 1, characterized in that it additionally comprises a step of separating insoluble lead dioxide from the lead-containing electrolyte, and reducing lead dioxide to lead oxide.
    [0004]
    4. METHOD, according to claim 3, characterized in that the step of reducing lead dioxide to lead oxide is carried out using sodium sulfite to produce sodium sulfate and lead oxide.
    [0005]
    5. METHOD, according to claim 4, characterized in that the sodium sulfate produced and the sodium sulfate solution are electrolyzed to produce sodium hydroxide and sulfuric acid, and in which the lead oxide is combined with the water based.
    [0006]
    6. METHOD, according to claim 1, characterized in that the precipitate containing lead hydroxide is dissolved in the concentrated aqueous base to convert all the lead hydroxide into soluble plumbite.
    [0007]
    7. METHOD, according to claim 1, characterized in that the step of continuously forming and removing adhering lead is carried out using a moving disk electrolyte.
    [0008]
    8. METHOD, according to claim 7, characterized in that the movement electrolyte is a rotating or alternative electrolyte.
    [0009]
    9. METHOD, according to claim 7, characterized in that the electrolyte comprises nickel-plated steel.
    [0010]
    10. METHOD, according to claim 1, characterized by the fact that the adhering lead has an apparent density less than 11 g/cm3 and that the lead in adhering lead has a purity of at least 99%.
    [0011]
    11. METHOD OF CONTINUOUS RECOVERY OF LEAD FROM A BATTERY PASTE COMPRISING LEAD OXIDES AND LEAD SULFATE characterized by the fact that the steps of: placing the battery paste in contact with an aqueous base to form a precipitate containing lead and a sodium sulfate solution; separating the lead-containing precipitate from the sodium sulfate solution; dissolving at least a portion of the lead-containing precipitate in an electrolyte fluid to generate an electrolyte containing lead and insoluble lead dioxide wherein the electrolyte fluid has a pH sufficient to form lead plumbite; Process the insoluble lead dioxide and sodium sulfate solution to generate components suitable for use in the step of bringing the battery paste into contact with the aqueous base by converting the sodium sulfate solution into a sodium hydroxide solution that forms at least part of the aqueous base; and continuously forming and removing adhering lead at pH on a moving electrode that comes into contact with the lead-containing electrolyte, wherein the lead has a purity of at least 95% by mol.
    [0012]
    12. METHOD, according to claim 11, characterized in that the aqueous base is added in an amount sufficient to produce lead carbonate or lead hydroxide from lead oxide.
    [0013]
    13. METHOD, according to claim 11, characterized in that the electrolyte fluid is selected from the group consisting of a sodium hydroxide solution, a sodium carbonate solution and a methanesulfonic acid solution.
    [0014]
    14. METHOD, according to claim 11, characterized in that the precipitate containing lead comprises lead hydroxide or lead carbonate, and additionally comprises lead dioxide.
    [0015]
    15. METHOD, according to claim 11, characterized in that it additionally comprises a step of separating insoluble lead dioxide from the lead-containing electrolyte, and reducing lead dioxide to lead oxide.
    [0016]
    16. METHOD, according to claim 11, characterized in that the processing step comprises a step of converting insoluble lead dioxide into lead oxide.
    [0017]
    17. METHOD, according to claim 16, characterized in that the lead oxide is placed in contact with the aqueous base, and in which a portion of the aqueous base is the sodium hydroxide solution.
    [0018]
    18. METHOD, according to claim 11, characterized in that the electrolyte fluid is the methanesulfonic acid solution, and in which the electrolyte comprises aluminum.
    [0019]
    19. METHOD, according to claim 11, characterized in that at least a portion of the lead-containing electrolyte after the continuous forming and removing step is treated to reduce a sodium ion concentration.
    [0020]
    20. METHOD, according to claim 11, characterized in that the adhering lead has an apparent density of less than 11 g/cm3 and that the lead in adhering lead has a purity of at least 99%.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112018011217B1|2022-01-18|METHODS OF CONTINUOUS RECOVERY OF LEAD FROM A BATTERY PASTE COMPRISING LEAD OXIDES AND LEAD SULFATE
    JP6805240B2|2020-12-23|Systems and methods for the recovery of lead from lead acid batteries
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    同族专利:
    公开号 | 公开日
    EP3384058A1|2018-10-10|
    JP6944453B2|2021-10-06|
    UA124145C2|2021-07-28|
    ZA201804384B|2020-07-29|
    JP2018538444A|2018-12-27|
    KR102096976B1|2020-05-27|
    US10316420B2|2019-06-11|
    KR20180080359A|2018-07-11|
    WO2017096209A1|2017-06-08|
    CA3007101C|2021-11-16|
    BR112018011217A2|2018-11-21|
    CA3007101A1|2017-06-08|
    EA201891307A1|2018-12-28|
    US20170159191A1|2017-06-08|
    PE20181184A1|2018-07-20|
    EA035532B1|2020-06-30|
    MX2018006737A|2018-08-01|
    EP3384058A4|2019-07-03|
    CL2018001459A1|2018-09-14|
    CN108603242B|2021-06-01|
    CN108603242A|2018-09-28|
    US11072864B2|2021-07-27|
    US20190301031A1|2019-10-03|
    AU2016362502B2|2021-08-12|
    AU2016362502A1|2018-07-19|
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    法律状态:
    2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-08-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-08-24| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    2021-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/12/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US14/957,026|2015-12-02|
    US14/957,026|US10316420B2|2015-12-02|2015-12-02|Systems and methods for continuous alkaline lead acid battery recycling|
    PCT/US2016/064697|WO2017096209A1|2015-12-02|2016-12-02|Systems and methods for continuous alkaline lead acid battery recycling|
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