# US 11,028,460 B2 · Systems and methods for recovery of lead from lead acid batteries > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,028,460 B2 - Document ID: US11028460B2 - Status: Granted - Kind: B2 - Application number: 15/573,356 - Filed: 2016-05-13 - Published: 2018-05-10 - Granted: 2021-06-08 - Earliest claimed: 2015-05-13 - Assignees: Aqua Metals Inc. - Applicants: Aqua Metals Inc. - Inventors: Robert Lewis Clarke; Brian Dougherty; Richard Clarke; Samaresh Mohanta - Web page: https://patentgrep.com/patent/US11028460B2 ## CPC - C22B 13/045: {Recovery from waste materials} - C25B 1/22: Inorganic acids - C25B 15/08: Supplying or removing reactants or electrolytes; Regeneration of electrolytes - C25C 1/18: of lead - H01M 10/06: Lead-acid accumulators (semi-lead accumulators H01M10/20) - H01M 10/54: Reclaiming serviceable parts of waste accumulators - Y02P 10/20: Recycling - Y02W 30/84: Recycling of batteries or fuel cells - C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS - C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B) - C25C: PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS - Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT ## Abstract Lead is recovered from lead paste of a lead acid battery in a continuous process. The lead paste is contacted with a base to generate a supernatant and a precipitate. The precipitate is separated from the supernatant, and is contacted with an alkane sulfonic acid to generate a mixture of lead ion solution and insoluble lead dioxide. The lead dioxide is reduced with a reducing agent to form lead oxide, and the lead oxide is combined with the lead ion solution to form a combined lead ion solution to so allow a continuous process without lead dioxide accumulation. Lead is recovered from the combined lead ion solution using electrolysis. ## Claims ### Claim 1 A method of recovering lead from a lead paste of a lead acid battery, wherein the lead paste comprises lead sulfate, the method comprising: contacting the lead paste with a base to thereby generate a supernatant comprising a soluble sulfate salt and a precipitate comprising an insoluble lead salt; separating the supernatant from the precipitate; contacting the precipitate with alkane sulfonic acid to generate a mixture comprising a lead ion solution and insoluble lead dioxide; contacting the insoluble lead dioxide in the precipitate or in the lead paste with a hydrogen peroxide to thereby reduce lead dioxide to lead oxide; combining the lead oxide with the lead ion solution to form a combined lead ion solution; applying an electrical potential to a cathode in contact with the combined lead ion solution to thereby continuously form adherent lead on a first portion of the cathode and to generate regenerated alkane sulfonic acid; wherein the adherent lead has a purity of at least 99.9%; and removing the adherent lead from a second portion of the cathode while continuously forming adherent lead on the first portion of the same cathode. ### Claim 2 (depends on 1) The method of claim 1, wherein the base is added in an amount sufficient to produce the supernatant comprising the soluble sulfate salt and the precipitate comprising the insoluble lead salt and to produce less than 0.1 mol % plumbate from the lead paste. ### Claim 3 (depends on 1) The method of claim 1, wherein the base comprises at least one of an alkali or alkaline earth metal hydroxide and a carbonate, and the insoluble lead salt comprises at least one of a lead oxide, a lead hydroxide, and a lead carbonate. ### Claim 4 (depends on 1) The method of claim 1, wherein the soluble sulfate salt comprises sodium sulfate, the base comprises sodium hydroxide, and the insoluble lead salt comprises lead hydroxide. ### Claim 5 (depends on 1) The method of claim 1, wherein the separating the supernatant from the precipitate is performed by at least one of settling, centrifugation, and filtration. ### Claim 6 (depends on 1) The method of claim 1, wherein the precipitate is substantially free of sulfate. ### Claim 7 (depends on 1) The method of claim 1, wherein the alkane sulfonic acid comprises methanesulfonic acid. ### Claim 8 (depends on 1) The method of claim 1, wherein the cathode exhibits rotational movement while the electrical potential is applied, such that the lead deposited on the cathode is removed from the combined lead ion solution. ### Claim 9 (depends on 1) The method of claim 1, wherein removing the adherent lead further comprises positioning a scraper near or at the second portion of the cathode to remove lead. ### Claim 10 (depends on 1) The method of claim 1, wherein the cathode comprises aluminum, an aluminum alloy, or an aluminum powder embedded in a plastic. ### Claim 11 (depends on 1) The method of claim 1, further comprising electrolyzing the supernatant comprising the soluble sulfate salt to produce a regenerated base and sulfuric acid. ### Claim 12 (depends on 11) The method of claim 11, wherein at least some of the base in the step of contacting the lead paste comprises the regenerated base. ### Claim 13 (depends on 1) The method of claim 1, wherein the combining the lead oxide further comprises feeding the lead oxide to the lead ion solution to thereby form the combined lead ion solution. ### Claim 14 (depends on 1) The method of claim 1, wherein the combining the lead oxide further comprises contacting the lead oxide with a second portion of the alkane sulfonic acid to thereby generate a second lead ion solution, and combining the lead ion solution and the second lead ion solution to form the combined lead ion solution.