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WO2015057189A1 - Recovery of high purity lead oxide from lead acid battery paste - Google Patents

Recovery of high purity lead oxide from lead acid battery paste Download PDF

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Publication number
WO2015057189A1
WO2015057189A1 PCT/US2013/064925 US2013064925W WO2015057189A1 WO 2015057189 A1 WO2015057189 A1 WO 2015057189A1 US 2013064925 W US2013064925 W US 2013064925W WO 2015057189 A1 WO2015057189 A1 WO 2015057189A1
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WO
WIPO (PCT)
Prior art keywords
lead
pbo
acid
hydroxide
treating
Prior art date
Application number
PCT/US2013/064925
Other languages
French (fr)
Inventor
W. Novis Smith
Steven KINSBURSKY
Original Assignee
Retriev Technologies Incorporated
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Publication date
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Priority to PCT/US2013/064925 priority Critical patent/WO2015057189A1/en
Publication of WO2015057189A1 publication Critical patent/WO2015057189A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/02—Oxides
    • C01G21/06—Lead monoxide [PbO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/12—Hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to the recovery of lead oxide (PbO) from spent lead acid battery paste through the preparation of a lead salt such as a lead carboxylate which is subsequently converted to PbO.
  • a lead salt such as a lead carboxylate
  • Russian Patent No. 2,398,758 to Pozhidaeva discloses a method of producing lead acetate by reacting lead metal and lead dioxide with acetic acid in the presence of an organic solvent and a stimulating iodine additive wherein lead dioxide is a reagent and oxidant with acetic acid to produce lead acetate.
  • U.S. Patent No. 4,222,769 discloses desulfurizing spent battery paste, which is then transformed into metallic lead by roasting in the presence of a carbon reducing agent.
  • U.S. Patent No. 4,769, 116 discloses treating exhausted lead-acid battery paste with sodium hydroxide to produce a solution of sodium sulfate and a desulfurized paste which is subjected to electrowinning to produce metallic lead.
  • U.S. Publication No. 2010/043600 to Martini discloses a process for the recovery of high purity lead compounds from electrode paste slime.
  • the process includes dissolving lead oxide in the paste in a suitable acid, reducing any insoluble lead dioxide with hydrogen peroxide, a sulfite or sulfurous anhydride, converting the lead oxide to lead sulfate and then treating the lead sulfate in a solution containing an acetate salt. The lead sulfate is then converted to a carbonate salt, oxide or hydroxide.
  • U.S. Patent Publication No. 2006/239903 discloses the production of lead hydrate or monoxide from residues containing lead in the form of sulfates, monoxides, etc. followed by the desulphurization of battery paste with a suitable carbonate or hydrate, calcinating the desulfurized material to get impure lead monoxide followed by leaching of the lead monoxide with acetic acid, followed by filtering and then treating the filtrate with an alkaline hydroxide to obtain a precipitate of lead hydrate or lead monoxide.
  • U.S. Patent No. 7,507,496 to Smith et al relates to the selective removal of sulfate from battery paste and recovering Pb 3 0 4 which has small amounts of impurities and can be separated from the impurities by dissolution.
  • the invention provides methods for producing high purity lead oxide
  • PbO from spent lead acid battery paste
  • a mixture of lead oxides e.g ., a mixture of Pb0 2 , PbO and Pb 3 0 4
  • the lead salt may be treated with a second base under an inert (C0 2 - free) atmosphere at an elevated temperature to form PbO.
  • At least one of the first base and second base may be an alkali hydroxide, such as an alkali hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonium hydroxide, or an alkali carbonate such as sodium carbonate or potassium carbonate. Mixtures of different bases may also be used.
  • the acid may be a carboxylic acid having 1-3 carbon atoms and may be selected from the group consisting of acetic acid, glycolic acid, formic acid, citric acid, lactic acid and combinations thereof.
  • the reducing agent may be selected from the group consisting of glyoxal, sorbitol, formaldehyde and acetaldehyde.
  • at least one lead salt may be selected from the group consisting of lead acetate, lead formate, lead lactate, lead citrate, lead glycolate and combinations thereof.
  • an amount of the first base is used which is effective to achieve a pH of at least about 10 while treating the spent lead acid battery paste with the first base.
  • the treating of the lead salt under an inert (C0 2 -free) atmosphere at an elevated temperature is carried out at a pH of at least about 12, wherein the inert atmosphere is generated from a gas selected from the group consisting of argon, nitrogen, C0 2 -free air and combinations thereof.
  • a sealed reactor may be used to protect the reaction mixture from C0 2 .
  • the elevated temperature may be at least about 70°C.
  • the PbO obtained has a purity of > 95%.
  • the invention provides methods that may further comprise treating the lead salt with sodium hydroxide at a pH of about 9 to about 11 to form lead hydroxide and heating the lead hydroxide at a temperature of at least about 90°C to form PbO.
  • One embodiment of the invention provides a method for producing high purity lead oxide (PbO) from spent lead acid battery paste comprising :
  • step b) reacting the mixture of lead oxides from step a) with a carboxylic acid having 1 to 3 carbon atoms and a reducing agent to form a water-soluble lead carboxylate;
  • step c) reacting the lead carboxylate from step b) under a C0 2 -free atmosphere at an elevated temperature with a second alkali hydroxide, which may be the same as or different from the first alkali hydroxide, to form PbO.
  • a second alkali hydroxide which may be the same as or different from the first alkali hydroxide
  • Another embodiment of the invention provides a method for recovering high purity lead oxide (PbO) from lead acid battery paste comprising :
  • step d) filtering the slurry from step d) to obtain a second filtrate comprised of lead acetate and a second filter cake;
  • step f) treating the second filtrate from step e) with sodium hydroxide under a C0 2 "free atmosphere at a pH of about 12 to obtain litharge (PbO) as a precipitate;
  • the PbO obtained by the process of the present invention may be combined with a desired amount of lead to provide a leady lead oxide.
  • a battery may comprise the PbO or leady lead oxide made by the methods described herein.
  • lead monoxide can be prepared in high yields and high purity from spent lead acid battery paste by a process that removes any sulfur containing compounds which is primarily all of the sulfate containing compounds.
  • the paste may be combined with water and treated with an alkali hydroxide at a pH of at least about 11 or preferably at least about 12 to provide a reaction mixture containing lead oxides (e.g., a mixture comprised of PbO, Pb0 2 and Pb 3 0 4 ) as solids and solubilized sulfur-containing species.
  • the reaction mixture may then be filtered to obtain a filtrate (comprising the solubilized sulfur-containing species) and a filter cake, with the filter cake being washed with water until the wash liquid has a pH of less than 9.
  • a filtrate comprising the solubilized sulfur-containing species
  • a filter cake is washed with water until the wash liquid has a pH of less than 9.
  • This procedure is effective to remove from the filter cake substantially all sulfates which may be present.
  • the lead oxides thereby obtained then undergo a reaction with an acid (e.g., acetic acid) and a reducing agent to yield a water-soluble lead salt (e.g., lead acetate).
  • an acid e.g., acetic acid
  • a reducing agent e.g., lead acetate
  • the lead oxides are dispersed in water and then combined with the acid and the reducing agent.
  • the reaction of the lead oxides with the acid and the reducing agent may be carried out at a somewhat elevated temperature, e.g., about 35°C to about 80°C, with stirring or other agitation of the mixture.
  • the reaction time generally may be from about 1 to about 6 hours.
  • nearly all the solids initially present in the mixture dissolve as a result of the formation of water-soluble lead salt.
  • any remaining solids may be separated from the lead salt solution by any suitable method such as filtration or centrifugation.
  • the lead salt may be treated with an alkali hydroxide (e.g., sodium hydroxide) according to the following reaction .
  • an alkali hydroxide e.g., sodium hydroxide
  • this reaction may alternatively yield lead hydroxide Pb(OH) 2 , which may be converted to PbO by heating at a high temperature.
  • the lead salt may be in the form of an aqueous solution, with the PbO or Pb(OH) 2 produced upon treatment with the alkali hydroxide precipitating from solution (whereby it can be readily isolated by filtration or other such suitable separation method).
  • the reaction of the lead salt with alkali hydroxide is carried out at a temperature of from about 70°C to about 110°C for about 15 to about 60 minutes.
  • the resulting slurry may be filtered while hot to obtain a filter cake comprised of PbO, which may be washed with water until the wash is neutral.
  • the alkali hydroxide used in the reaction preferably is concentrated (e.g., in the form of an aqueous solution containing at least about 40% by weight alkali hydroxide), so that the initial concentration of alkali hydroxide in the reaction mixture is also relatively high (typically, the alkali hydroxide reagent will be diluted somewhat upon mixing with the solution of lead salt).
  • the product initially formed from the lead salt is Pb(OH) 2 , which may be similarly isolated by filtration of the reaction mixture and then heated at a high temperature (e.g., 250°C for 1-3 hours) to obtain PbO.
  • the present process may comprise the steps of: treating spent lead battery paste with an alkali hydroxide so as to remove any sulfates in solution and to obtain a lead oxide mixture comprised of PbO, Pb0 2 and Pb 3 0 4 in the form of solids; reacting the lead oxide mixture with a carboxylic acid having 1-3 carbon atoms in the presence of a reducing agent to form a water-soluble lead salt (e.g., a lead carboxylate) ; isolating the lead salt (in the form of an aqueous solution, for example) and reacting it with concentrated alkali hydroxide at a temperature of 50-100°C under a C0 2 -free atmosphere at a pH of at least 10 to obtain pure litharge (PbO).
  • an alkali hydroxide so as to remove any sulfates in solution and to obtain a lead oxide mixture comprised of PbO, Pb0 2 and Pb 3 0 4 in the form of solids
  • the step of treating spent lead battery paste with a base such as an alkali hydroxide may be carried out at a pH of at least 10, or at least about 11, or at least about 12 or at least about 13 and at an elevated temperature, such as between 50°C-100°C, for a time effective to achieve the desired level of conversion to lead oxides (e.g., from about 1 to about 5 hours).
  • the inert atmosphere employed when reacting the lead salt with alkali hydroxide may be generated from argon, nitrogen, or C0 2 -free air so as to protect the reaction from carbon dioxide.
  • the lead oxide mixture has microscopic small amounts of insoluble antimony/lead alloy pieces (-325 mesh) and barium sulfate (about 0.3% barium and about 0.5% antimony depending on the battery sources and crushing method).
  • the mixed lead oxides should be dissolved away from these impurities which can then be filtered off from the solution of the soluble lead salt, such as lead acetate. Only PbO is soluble in acetic acid and the Pb 3 0 4 and Pb0 2 must be reduced to PbO to be soluble. Any process which does this should be low cost and require minimum energy since the process must compete with currently used smelting processes.
  • the bases used herein may be alkali hydroxides and/or alkali carbonates.
  • the bases used herein may be selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate and potassium carbonate. More preferably, the bases are either sodium hydroxide, sodium carbonate or potassium hydroxide.
  • the acids used herein may be organic acids selected from the group consisting of acetic acid, glycolic acid, formic acid, citric acid, lactic acid and combinations thereof.
  • the acid is a carboxylic acid such as acetic acid.
  • the acid may be recycled following conversion of the lead salt to PbO.
  • the reducing agents used herein may be selected from the group consisting of glyoxal, sorbitol, formaldehyde, aceta dehyde, soluble cellulosic material and combinations thereof.
  • the reducing agent is either glyoxal or sorbitol.
  • the water-soluble lead salts herein may be selected from the group consisting of lead acetate, lead formate, lead lactate, lead citrate, lead glycolate and combinations thereof.
  • the lead salt is lead acetate.
  • the percentage of the ingredients used herein is "by weight".
  • the spent battery paste can be obtained from spent battery paste as disclosed in U.S. Patent No. 7,507,496, the disclosure of which is herein incorporated by reference in its entirety for all purposes. It has further been found that the 100% litharge (orange form) which is produced under the preferred conditions of the present invention can be mixed with 25% by weight molten lead metal under nitrogen or inert atmosphere with vigorous stirring to quickly produce the preferred industrial starting material for making lead acid battery electrodes called leady oxide or leady lead oxide. This material is usually produced commercially in a Barton reactor or ball mill at 480-550°C in air, requiring many hours of stirring and heating resulting in excessive heat and energy.
  • the damp washed dark red cake (free of essentially all the sulfate) was dispersed in 1600 ml of water in the 2-liter PFA plastic wide mouth jar with stirrer which was again used as the reactor. This mixture was stirred and 280 g of acetic acid was added. 150 g of 40% glyoxal were then added carefully. A slight exotherm was noted. The mixture was heated at 40°O60°C with stirring until the paste turned gray and almost completely dissolved leaving about 6% gray particulate in the slurry. This step took 3 hours. The slurry was filtered warm (40°C-50°C) using plastic filter flask and the filter cake washed.
  • the gray black filter cake weighed about 35 g and contained 8% antimony, 50% lead, and 5% barium.
  • the clear pale yellow filtrate contained >90% recovery of the original lead as lead acetate (No silica or glass was used in processing in order to minimize silica contamination, which interferes with conversion of lead acetate to pure litharge with no massicot phase).
  • the filtrate was heated to about 70°C and then poured into a 2-1 PFA reactor (90°C) with good stirring and containing 520 g of 50% NaOH at >85°C under nitrogen to protect it from carbon dioxide and some cooling was necessary to maintain the temperature below 105°C.
  • the pH was monitored so that only enough extra NaOH was added to maintain the pH at about 12.
  • the slurry was heated for 30 minutes at 105°C and then filtered hot.
  • the orange litharge cake was washed until neutrality and then dried to produce PbO (e.g., litharge) with high purity.
  • the yield was 290 g (90%) based on the starting lead content in the lead acid battery paste with the sodium ⁇ 30 ppm.
  • the resulting dull red brown filter cake was suspended in 600 ml water in a 1-1 polypropylene reaction flask with stirring and 180 g acetic acid added. Then 15 g of 40% glyoxal was added. The mixture was slightly exothermic and warmed to 40°C. 32 g more of 40% glyoxal was added and heated to 67°C with some exothermic reaction assisting and some foaming. The mixture was heated at 67-75°C for 4 hours, cooled to 25°C and filtered to obtain a filtrate and a filter cake. The gray insoluble filter cake containing the impurities weighed 19 g when dry and analysis showed barium 5.28%; antimony 8.00%; lead 53.0%.
  • Example 1 The lead acetate filtrate solution of Example 1 was alternatively added slowly to a 2-1 PFA reactor (no heating required) equipped with good stirring under nitrogen. 520 g of dilute IMaOH was slowly added with good stirring to yield a slurry. Some cooling was applied to maintain the temperature below 25°C. The pH was monitored so that only enough NaOH was added to achieve a pH of 10.5 at the finish. The slurry was filtered to obtain a filtrate and a filter cake. The cake was washed and then dried at below 50°C to produce lead hydroxide, Pb(OH) 2 . The lead hydroxide was heated in a furnace at 250°C for about 2 hours to convert it to PbO, litharge.
  • Example 1 The concentrated lead acetate solution of Example 1 was poured directly into a hot aqueous solution containing at least 5% excess sodium or potassium hydroxide to directly form high purity PbO, litharge.

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  • Inorganic Chemistry (AREA)
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Abstract

The invention relates to the low temperature recovery of lead oxide (PbO) from lead acid battery paste through the preparation of at least one lead salt such as a lead carboxylate from the battery paste and the conversion of the at least one lead salt to PbO. The methods described herein may comprise treating the spent lead acid battery paste with a first base to remove sulfates and to form a mixture of lead oxides; treating the lead oxide mixture with an acid and a reducing agent to form at least one lead salt; and treating the lead salt with a second base under a CO2-free atmosphere at an elevated temperature to form PbO.

Description

RECOVERY OF HIGH PURITY LEAD OXIDE FROM
LEAD ACID BATTERY PASTE
Field of Invention
The invention relates to the recovery of lead oxide (PbO) from spent lead acid battery paste through the preparation of a lead salt such as a lead carboxylate which is subsequently converted to PbO.
Background of the Invention
The recovery of high purity lead oxide materials (99.99+%) from lead acid pastes has been a long standing requirement with lead battery manufacturers. The lead has value as a high purity material. Currently the commercial practice is to send this paste recovered from crushing lead batteries to the lead smelters who separately process this mix of red lead, lead sulfate with carbon to obtain a crude lead metal product. This lead metal is then separately reacted with flux and air to remove the contaminating impurities such as antimony, barium, calcium, sulfur, copper, arsenic and other materials.
Russian Patent No. 2,398,758 to Pozhidaeva discloses a method of producing lead acetate by reacting lead metal and lead dioxide with acetic acid in the presence of an organic solvent and a stimulating iodine additive wherein lead dioxide is a reagent and oxidant with acetic acid to produce lead acetate.
U.S. Patent No. 4,222,769 discloses desulfurizing spent battery paste, which is then transformed into metallic lead by roasting in the presence of a carbon reducing agent.
U.S. Patent No. 4,769, 116 discloses treating exhausted lead-acid battery paste with sodium hydroxide to produce a solution of sodium sulfate and a desulfurized paste which is subjected to electrowinning to produce metallic lead.
International Publication No. W099/44942 discloses a process of producing lead monoxide from spent led battery paste using fluxing agents and an organic reducing agent in a calcination step at a temperature of 400°C-450°C.
U.S. Publication No. 2010/043600 to Martini discloses a process for the recovery of high purity lead compounds from electrode paste slime. The process includes dissolving lead oxide in the paste in a suitable acid, reducing any insoluble lead dioxide with hydrogen peroxide, a sulfite or sulfurous anhydride, converting the lead oxide to lead sulfate and then treating the lead sulfate in a solution containing an acetate salt. The lead sulfate is then converted to a carbonate salt, oxide or hydroxide.
U.S. Patent Publication No. 2006/239903 discloses the production of lead hydrate or monoxide from residues containing lead in the form of sulfates, monoxides, etc. followed by the desulphurization of battery paste with a suitable carbonate or hydrate, calcinating the desulfurized material to get impure lead monoxide followed by leaching of the lead monoxide with acetic acid, followed by filtering and then treating the filtrate with an alkaline hydroxide to obtain a precipitate of lead hydrate or lead monoxide.
U.S. Patent No. 7,507,496 to Smith et al relates to the selective removal of sulfate from battery paste and recovering Pb304 which has small amounts of impurities and can be separated from the impurities by dissolution.
The prior art methods get high yields of lead oxide at the expense of purity or in the alternate high purity at the expense of yield. It is therefore desirable to obtain both high yield and high purity when treating spent acid battery paste to obtain lead oxide. Summary of the Invention
In one aspect, the invention provides methods for producing high purity lead oxide
(PbO) from spent lead acid battery paste comprising treating the spent lead acid battery paste with a first base to form a mixture of lead oxides (e.g ., a mixture of Pb02, PbO and Pb304) and treating the lead oxide mixture with an acid and a reducing agent to form at least one lead salt, which is typically water-soluble and obtained in the form of an aqueous solution. The lead salt may be treated with a second base under an inert (C02- free) atmosphere at an elevated temperature to form PbO. At least one of the first base and second base may be an alkali hydroxide, such as an alkali hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonium hydroxide, or an alkali carbonate such as sodium carbonate or potassium carbonate. Mixtures of different bases may also be used.
In another aspect, the acid may be a carboxylic acid having 1-3 carbon atoms and may be selected from the group consisting of acetic acid, glycolic acid, formic acid, citric acid, lactic acid and combinations thereof. In another aspect, the reducing agent may be selected from the group consisting of glyoxal, sorbitol, formaldehyde and acetaldehyde. In another aspect, at least one lead salt may be selected from the group consisting of lead acetate, lead formate, lead lactate, lead citrate, lead glycolate and combinations thereof.
In a further aspect, an amount of the first base is used which is effective to achieve a pH of at least about 10 while treating the spent lead acid battery paste with the first base. In a further aspect, the treating of the lead salt under an inert (C02-free) atmosphere at an elevated temperature is carried out at a pH of at least about 12, wherein the inert atmosphere is generated from a gas selected from the group consisting of argon, nitrogen, C02-free air and combinations thereof. A sealed reactor may be used to protect the reaction mixture from C02. In a further aspect, the elevated temperature may be at least about 70°C. In a further aspect, the PbO obtained has a purity of > 95%.
In yet a further aspect, the invention provides methods that may further comprise treating the lead salt with sodium hydroxide at a pH of about 9 to about 11 to form lead hydroxide and heating the lead hydroxide at a temperature of at least about 90°C to form PbO. One embodiment of the invention provides a method for producing high purity lead oxide (PbO) from spent lead acid battery paste comprising :
a) reacting lead acid battery paste with a first alkali hydroxide to remove sulfates and to form a mixture of lead oxides;
b) reacting the mixture of lead oxides from step a) with a carboxylic acid having 1 to 3 carbon atoms and a reducing agent to form a water-soluble lead carboxylate;
c) reacting the lead carboxylate from step b) under a C02-free atmosphere at an elevated temperature with a second alkali hydroxide, which may be the same as or different from the first alkali hydroxide, to form PbO.
Another embodiment of the invention provides a method for recovering high purity lead oxide (PbO) from lead acid battery paste comprising :
a) reacting lead acid battery paste with sodium hydroxide at a temperature of from about 60°C to about 70°C at a pH greater than about 12 to obtain a first slurry; b) filtering the slurry from step a) to obtain a first filtrate and a first filter cake; c) reacting the first filter cake from step b) with acetic acid to form a product; d) treating the product from step c) with glyoxal to form a slurry comprising a solution of lead acetate;
e) filtering the slurry from step d) to obtain a second filtrate comprised of lead acetate and a second filter cake;
f) treating the second filtrate from step e) with sodium hydroxide under a C02"free atmosphere at a pH of about 12 to obtain litharge (PbO) as a precipitate;
g) recovering the litharge (PbO) from step f) by filtration.
The PbO obtained by the process of the present invention may be combined with a desired amount of lead to provide a leady lead oxide.
In yet a further aspect, a battery may comprise the PbO or leady lead oxide made by the methods described herein.
Detailed Description of the Invention
According to the present invention, lead monoxide (PbO) can be prepared in high yields and high purity from spent lead acid battery paste by a process that removes any sulfur containing compounds which is primarily all of the sulfate containing compounds. The paste may be combined with water and treated with an alkali hydroxide at a pH of at least about 11 or preferably at least about 12 to provide a reaction mixture containing lead oxides (e.g., a mixture comprised of PbO, Pb02 and Pb304) as solids and solubilized sulfur-containing species. The reaction mixture may then be filtered to obtain a filtrate (comprising the solubilized sulfur-containing species) and a filter cake, with the filter cake being washed with water until the wash liquid has a pH of less than 9. This procedure is effective to remove from the filter cake substantially all sulfates which may be present. The lead oxides thereby obtained then undergo a reaction with an acid (e.g., acetic acid) and a reducing agent to yield a water-soluble lead salt (e.g., lead acetate). The following equation illustrates the reaction of Pb304 with acetic acid in the presence of a reducing agent to form lead acetate.
Pb304 + acetic acid + reducing agent ---> Pb(C02CH3)2 (solution)
In one embodiment of the invention, the lead oxides are dispersed in water and then combined with the acid and the reducing agent. The reaction of the lead oxides with the acid and the reducing agent may be carried out at a somewhat elevated temperature, e.g., about 35°C to about 80°C, with stirring or other agitation of the mixture. The reaction time generally may be from about 1 to about 6 hours. Typically, nearly all the solids initially present in the mixture dissolve as a result of the formation of water-soluble lead salt. When the reaction has been carried out for the desired length of time (typically about 1 to about 5 hours), any remaining solids may be separated from the lead salt solution by any suitable method such as filtration or centrifugation.
The lead salt may be treated with an alkali hydroxide (e.g., sodium hydroxide) according to the following reaction . Depending upon the conditions used, this reaction may alternatively yield lead hydroxide Pb(OH)2, which may be converted to PbO by heating at a high temperature.
Pb(C02CH3)2 + 2NaOH — -> PbO + 2Na(C02CH3)
The lead salt may be in the form of an aqueous solution, with the PbO or Pb(OH)2 produced upon treatment with the alkali hydroxide precipitating from solution (whereby it can be readily isolated by filtration or other such suitable separation method). In one embodiment of the invention, the reaction of the lead salt with alkali hydroxide is carried out at a temperature of from about 70°C to about 110°C for about 15 to about 60 minutes. The resulting slurry may be filtered while hot to obtain a filter cake comprised of PbO, which may be washed with water until the wash is neutral. The alkali hydroxide used in the reaction preferably is concentrated (e.g., in the form of an aqueous solution containing at least about 40% by weight alkali hydroxide), so that the initial concentration of alkali hydroxide in the reaction mixture is also relatively high (typically, the alkali hydroxide reagent will be diluted somewhat upon mixing with the solution of lead salt). Under certain conditions (such as when a more dilute solution of alkali hydroxide is used and/or when the pH of the reaction mixture is relatively low, e.g., about 9 to about 11), the product initially formed from the lead salt is Pb(OH)2, which may be similarly isolated by filtration of the reaction mixture and then heated at a high temperature (e.g., 250°C for 1-3 hours) to obtain PbO. More particularly the present process may comprise the steps of: treating spent lead battery paste with an alkali hydroxide so as to remove any sulfates in solution and to obtain a lead oxide mixture comprised of PbO, Pb02 and Pb304 in the form of solids; reacting the lead oxide mixture with a carboxylic acid having 1-3 carbon atoms in the presence of a reducing agent to form a water-soluble lead salt (e.g., a lead carboxylate) ; isolating the lead salt (in the form of an aqueous solution, for example) and reacting it with concentrated alkali hydroxide at a temperature of 50-100°C under a C02-free atmosphere at a pH of at least 10 to obtain pure litharge (PbO).
The step of treating spent lead battery paste with a base such as an alkali hydroxide may be carried out at a pH of at least 10, or at least about 11, or at least about 12 or at least about 13 and at an elevated temperature, such as between 50°C-100°C, for a time effective to achieve the desired level of conversion to lead oxides (e.g., from about 1 to about 5 hours).
The inert atmosphere employed when reacting the lead salt with alkali hydroxide may be generated from argon, nitrogen, or C02-free air so as to protect the reaction from carbon dioxide. The lead oxide mixture has microscopic small amounts of insoluble antimony/lead alloy pieces (-325 mesh) and barium sulfate (about 0.3% barium and about 0.5% antimony depending on the battery sources and crushing method). Furthermore, the mixed lead oxides should be dissolved away from these impurities which can then be filtered off from the solution of the soluble lead salt, such as lead acetate. Only PbO is soluble in acetic acid and the Pb304 and Pb02 must be reduced to PbO to be soluble. Any process which does this should be low cost and require minimum energy since the process must compete with currently used smelting processes.
It is advantageous to remove the sulfate first to avoid contaminating any downstream processing with sulfate and sulfur. This may be most efficient if performed by first converting the insoluble sulfate-containing lead oxide mixture to a sulfate-free lead oxide mixture and then converting the sulfate-free lead oxide mixture to soluble lead (II) salt in one step by adding a reducing agent at the same time as when the solubilizing acid is added to an agitated aqueous suspension of the essentially sulfur free (sulfate free) lead oxide mixture (less than 0.6% by weight sulfate). The stirred warmed slurry turns from red to gray and almost (>91%) all of the lead dissolves to form a solution of lead salt. This solution is filtered to remove any insolubles, with the filter cake thereby obtained containing impurities, such as antimony, barium sulfate and with about 50% lead in the resulting filter cake as insoluble lead/antimony alloy powder.
The bases used herein may be alkali hydroxides and/or alkali carbonates.
Preferably, the bases used herein may be selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate and potassium carbonate. More preferably, the bases are either sodium hydroxide, sodium carbonate or potassium hydroxide.
The acids used herein may be organic acids selected from the group consisting of acetic acid, glycolic acid, formic acid, citric acid, lactic acid and combinations thereof. Preferably, the acid is a carboxylic acid such as acetic acid. The acid may be recycled following conversion of the lead salt to PbO.
The reducing agents used herein may be selected from the group consisting of glyoxal, sorbitol, formaldehyde, aceta dehyde, soluble cellulosic material and combinations thereof. Preferably, the reducing agent is either glyoxal or sorbitol.
The water-soluble lead salts herein may be selected from the group consisting of lead acetate, lead formate, lead lactate, lead citrate, lead glycolate and combinations thereof. Preferably, the lead salt is lead acetate.
The percentage of the ingredients used herein is "by weight". The spent battery paste can be obtained from spent battery paste as disclosed in U.S. Patent No. 7,507,496, the disclosure of which is herein incorporated by reference in its entirety for all purposes. It has further been found that the 100% litharge (orange form) which is produced under the preferred conditions of the present invention can be mixed with 25% by weight molten lead metal under nitrogen or inert atmosphere with vigorous stirring to quickly produce the preferred industrial starting material for making lead acid battery electrodes called leady oxide or leady lead oxide. This material is usually produced commercially in a Barton reactor or ball mill at 480-550°C in air, requiring many hours of stirring and heating resulting in excessive heat and energy. The actual final composition from these commercial processes is difficult to control due to the many variables involved so that the actual composition range will run 15-30% lead metal content. In addition, it is preferred to have 100% of the PbO as the litharge form, but in practice, higher temperature massicot (yellow-white) form is also present due to the excessive heating required. This new process of taking very pure 100% litharge and mixing with molten lead metal at 400- 450° under nitrogen to prevent any oxidation of the lead while the rapid quick mixing occurs is a major step forward for achieving a low cost, very high purity material with a precise composition which is desired by the lead acid battery manufacturers. This new leady oxide material which has not been available before due to the high cost by other routes, lack of control, and need for the high purity litharge produced by this process is an important advance for the lead acid battery industry.
Not only do the methods described herein save significant energy and reduce sulfur emissions compared to smelter recycling, but they also produce a very pure and highly desired oxide of lead at lower cost. EXAMPLE 1
340 g equivalent dry solids (e.g., as the damp or slurry (-170 mesh) lead paste from the lead battery breaker and 1-liter water) were added to the 2-1 PFA paste wide mouth jar with stirrer used as a reactor. A heating tape was wrapped around this container to provide a means of heating this reactor to 60-70°C. Approximately 146 g of 50% NaOH solution were carefully added and the pH checked (should be 12 or greater). The mixture was stirred and heated and the pH was adjusted with small amounts of additional NaOH solution to maintain the pH > 11 as the reaction mixture was heated and stirred for 3 hours. The slurry was filtered to provide a filtrate and a filter cake, with the cake being washed until the wash was below pH 9. The damp washed dark red cake (free of essentially all the sulfate) was dispersed in 1600 ml of water in the 2-liter PFA plastic wide mouth jar with stirrer which was again used as the reactor. This mixture was stirred and 280 g of acetic acid was added. 150 g of 40% glyoxal were then added carefully. A slight exotherm was noted. The mixture was heated at 40°O60°C with stirring until the paste turned gray and almost completely dissolved leaving about 6% gray particulate in the slurry. This step took 3 hours. The slurry was filtered warm (40°C-50°C) using plastic filter flask and the filter cake washed. (The gray black filter cake weighed about 35 g and contained 8% antimony, 50% lead, and 5% barium.) The clear pale yellow filtrate contained >90% recovery of the original lead as lead acetate (No silica or glass was used in processing in order to minimize silica contamination, which interferes with conversion of lead acetate to pure litharge with no massicot phase).
The filtrate was heated to about 70°C and then poured into a 2-1 PFA reactor (90°C) with good stirring and containing 520 g of 50% NaOH at >85°C under nitrogen to protect it from carbon dioxide and some cooling was necessary to maintain the temperature below 105°C. The pH was monitored so that only enough extra NaOH was added to maintain the pH at about 12. The slurry was heated for 30 minutes at 105°C and then filtered hot. The orange litharge cake was washed until neutrality and then dried to produce PbO (e.g., litharge) with high purity. The yield was 290 g (90%) based on the starting lead content in the lead acid battery paste with the sodium < 30 ppm.
EXAMPLE 2
339 g dry lead acid battery breaker paste (-170 mesh) was added to 400 ml water and stirred in a PFA beaker. (This was a mixture of lead sulfate, red lead and impurities, primarily 0.3% barium as barium sulfate and 0.5% antimony as complex lead alloy and insoluble compounds. The lead content was 78.1% or 265 g lead.) To this slurry was added 73 g of 50% sodium hydroxide and the slurry heated to 90°C for 3 hours. The slurry was cooled and filtered to obtain a filtrate and a filter cake, with the filter cake being washed free of base with water. The resulting dull red brown filter cake was suspended in 600 ml water in a 1-1 polypropylene reaction flask with stirring and 180 g acetic acid added. Then 15 g of 40% glyoxal was added. The mixture was slightly exothermic and warmed to 40°C. 32 g more of 40% glyoxal was added and heated to 67°C with some exothermic reaction assisting and some foaming. The mixture was heated at 67-75°C for 4 hours, cooled to 25°C and filtered to obtain a filtrate and a filter cake. The gray insoluble filter cake containing the impurities weighed 19 g when dry and analysis showed barium 5.28%; antimony 8.00%; lead 53.0%.
To the stirred clear pale yellow filtrate solution in a polypropylene container was added 160 g 50% sodium hydroxide with stirring to bring the pH to 10-11 to obtain litharge PbO.
EXAMPLE 3
The lead acetate filtrate solution of Example 1 was alternatively added slowly to a 2-1 PFA reactor (no heating required) equipped with good stirring under nitrogen. 520 g of dilute IMaOH was slowly added with good stirring to yield a slurry. Some cooling was applied to maintain the temperature below 25°C. The pH was monitored so that only enough NaOH was added to achieve a pH of 10.5 at the finish. The slurry was filtered to obtain a filtrate and a filter cake. The cake was washed and then dried at below 50°C to produce lead hydroxide, Pb(OH)2. The lead hydroxide was heated in a furnace at 250°C for about 2 hours to convert it to PbO, litharge.
EXAMPLE 4
The concentrated lead acetate solution of Example 1 was poured directly into a hot aqueous solution containing at least 5% excess sodium or potassium hydroxide to directly form high purity PbO, litharge.
While this invention has been described in terms of several preferred embodiments, there are alterations, permutations, and substitute equivalents, which fall within the scope of this invention. It should also be noted that there are many alternative ways of implementing the methods and apparatuses of the present invention. It is therefore intended that the following appended claims be interpreted as including all such alterations, permutations, and substitute equivalents as fall within the true spirit and scope of the present invention.

Claims

What is claimed is:
1. A method for producing high purity lead oxide (PbO) from spent lead acid battery paste comprising :
treating the spent lead acid battery paste with a first base to form a sulfate-free lead oxide mixture;
treating the sulfate-free lead oxide mixture with an acid and a reducing agent to form at least one water-soluble lead salt.
2. The method of Claim 1, further comprising treating the water-soluble lead salt with a second base under a C02-free atmosphere at an elevated temperature to form PbO.
3. The method of Claim 1, further comprising treating the water-soluble lead salt with sodium hydroxide at a pH of about 9 to about 11 to form lead hydroxide.
4. The method of Claim 1, wherein the first base is selected from the group consisting of alkali hydroxides, alkali carbonates and combinations thereof.
5. The method of Claim 1, wherein the first base is sodium hydroxide.
6.· The method of Claim 1, wherein the first base is sodium carbonate.
7. The method of Claim 1, wherein the acid is a carboxylic acid having 1-3 carbon atoms.
8, The method of Claim 1, wherein the acid is selected from the group consisting of acetic acid, glycolic acid, formic acid, citric acid, lactic acid and combinations thereof.
9. The method of Claim 1, wherein the acid is acetic acid.
10. The method of Claim 1, wherein the reducing agent is selected from the group consisting of glyoxal, sorbitol, formaldehyde and acetaldehyde.
11. The method of Claim 1, wherein the reducing agent is glyoxal.
12. The method of Claim 1, wherein the at least one water-soluble lead salt is selected from the group consisting of lead acetate, lead formate, lead lactate, lead citrate, lead glycolate and combinations thereof.
13. The method of Claim 1, wherein the at least one water-soluble lead salt is lead acetate.
14. The method of Claim 1, wherein an amount of the first base is used which is effective to achieve a pH of at least about 10.
15. The method of Claim 2, wherein treating the water-soluble lead salt under a C02- free atmosphere at an elevated temperature is carried out at a pH of at least about 11.
16. The method of Claim 2, wherein the C02-free atmosphere is generated from a gas selected from the group consisting of argon, nitrogen, C02-free air and combinations thereof.
17. The method of Claim 2, wherein the elevated temperature is at least about 60°C.
18. The method of Claim 2, wherein the PbO has a purity of > 95%.
19. The method of Claim 3, further comprising heating the lead hydroxide at a temperature of at least about 150°C to form PbO.
20. The method of Claim 2, wherein the second base is selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonium hydroxide.
21. A method for producing high purity lead oxide (PbO) from spent lead acid battery paste comprising :
a) reacting lead acid battery paste with a first alkali hydroxide to remove sulfates and to form a mixture of lead oxides;
b) reacting the mixture of lead oxides from step a) with a carboxylic acid having 1 to 3 carbon atoms and a reducing agent to form a lead carboxylate;
c) reacting the lead carboxylate from step b) under a C02-free atmosphere at an elevated temperature with a second alkali hydroxide, which may be the same as or different from the first alkali hydroxide, to form PbO.
22. A method for recovering high purity lead oxide (PbO) from lead acid battery paste comprising :
a) reacting lead acid battery paste with sodium hydroxide at a temperature of from about 60°C to about 70°C at a pH greater than about 10 to obtain a first slurry; b) filtering the slurry from step a) to obtain a first filtrate and a first filter cake; c) reacting the first filter cake from step b) with acetic acid to form a product; d) treating the product from step c) with glyoxal to form a slurry containing a solution of lead acetate;
e) filtering the slurry from step d) to obtain a second filtrate comprised of lead acetate and a second filter cake;
f) treating the second filtrate from step e) with sodium hydroxide under a nitrogen atmosphere at a pH of about 12 to obtain litharge (PbO) as a precipitate;
g) recovering the litharge (PbO) from step f) by filtration.
23. The method of claim 2, comprising an additional step of mixing the PbO formed with about 10% to about 30% by weight lead, based on the total weight of PbO and lead, to form leady lead oxide.
24. A battery comprising the PbO made by the method of claim 1.
25. A battery comprising the leady lead oxide made by the method of claim 23.
PCT/US2013/064925 2013-10-15 2013-10-15 Recovery of high purity lead oxide from lead acid battery paste WO2015057189A1 (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016183428A1 (en) * 2015-05-13 2016-11-17 Aqua Metals Inc. Systems and methods for recovery of lead from lead acid batteries
WO2017096209A1 (en) 2015-12-02 2017-06-08 Aqua Metals Inc. Systems and methods for continuous alkaline lead acid battery recycling
WO2017105551A1 (en) * 2015-12-14 2017-06-22 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
US9837689B2 (en) 2013-11-19 2017-12-05 Aqua Metals Inc. Method for smelterless recycling of lead acid batteries
WO2020025970A1 (en) * 2018-08-03 2020-02-06 Imperial College Of Science, Technology And Medicine Recycling of lead- and tin-based materials
US10689769B2 (en) 2015-05-13 2020-06-23 Aqua Metals Inc. Electrodeposited lead composition, methods of production, and uses
US10793957B2 (en) 2015-05-13 2020-10-06 Aqua Metals Inc. Closed loop systems and methods for recycling lead acid batteries
GB2586582A (en) * 2019-08-12 2021-03-03 Aeg Holdings Ltd Desulfurisation of lead-containing waste

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7507496B1 (en) * 2004-12-07 2009-03-24 Toxco, Inc Process for recovering lead oxides from exhausted batteries
US20100143219A1 (en) * 2007-01-05 2010-06-10 Tai-Kwong-Yokohama Battery Industried Sdn Bhd Process for the production of nano lead oxides
CN101899576A (en) * 2010-04-30 2010-12-01 浙江汇同电源有限公司 Method for recycling lead from lead-acid battery paste
US8323376B2 (en) * 2006-11-08 2012-12-04 Cambridge Enterprise Limited Lead recycling
US8323595B1 (en) * 2011-09-03 2012-12-04 Toxco, Inc. Recovery of high purity lead oxide from lead acid battery paste

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7507496B1 (en) * 2004-12-07 2009-03-24 Toxco, Inc Process for recovering lead oxides from exhausted batteries
US8323376B2 (en) * 2006-11-08 2012-12-04 Cambridge Enterprise Limited Lead recycling
US20100143219A1 (en) * 2007-01-05 2010-06-10 Tai-Kwong-Yokohama Battery Industried Sdn Bhd Process for the production of nano lead oxides
CN101899576A (en) * 2010-04-30 2010-12-01 浙江汇同电源有限公司 Method for recycling lead from lead-acid battery paste
US8323595B1 (en) * 2011-09-03 2012-12-04 Toxco, Inc. Recovery of high purity lead oxide from lead acid battery paste

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10340561B2 (en) 2013-11-19 2019-07-02 Aqua Metals Inc. Devices and method for smelterless recycling of lead acid batteries
US11239507B2 (en) 2013-11-19 2022-02-01 Aqua Metals Inc. Devices and method for smelterless recycling of lead acid batteries
US10665907B2 (en) 2013-11-19 2020-05-26 Aqua Metals Inc. Devices and method for smelterless recycling of lead acid batteries
US9837689B2 (en) 2013-11-19 2017-12-05 Aqua Metals Inc. Method for smelterless recycling of lead acid batteries
KR102274210B1 (en) 2015-05-13 2021-07-06 아쿠아 메탈스 인크. Systems and methods for recovery of lead from lead acid batteries
US11028460B2 (en) 2015-05-13 2021-06-08 Aqua Metals Inc. Systems and methods for recovery of lead from lead acid batteries
WO2016183428A1 (en) * 2015-05-13 2016-11-17 Aqua Metals Inc. Systems and methods for recovery of lead from lead acid batteries
KR20180012779A (en) * 2015-05-13 2018-02-06 아쿠아 메탈스 인크. Systems and methods for recovery of lead from lead-acid batteries
US10793957B2 (en) 2015-05-13 2020-10-06 Aqua Metals Inc. Closed loop systems and methods for recycling lead acid batteries
US10689769B2 (en) 2015-05-13 2020-06-23 Aqua Metals Inc. Electrodeposited lead composition, methods of production, and uses
US10316420B2 (en) 2015-12-02 2019-06-11 Aqua Metals Inc. Systems and methods for continuous alkaline lead acid battery recycling
US11072864B2 (en) 2015-12-02 2021-07-27 Aqua Metals Inc. Systems and methods for continuous alkaline lead acid battery recycling
WO2017096209A1 (en) 2015-12-02 2017-06-08 Aqua Metals Inc. Systems and methods for continuous alkaline lead acid battery recycling
WO2017105551A1 (en) * 2015-12-14 2017-06-22 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
US10062933B2 (en) 2015-12-14 2018-08-28 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
WO2020025970A1 (en) * 2018-08-03 2020-02-06 Imperial College Of Science, Technology And Medicine Recycling of lead- and tin-based materials
CN112534071A (en) * 2018-08-03 2021-03-19 帝国科学、技术与医学学院 Recovery of lead and tin materials
US11427478B2 (en) 2018-08-03 2022-08-30 Imperial College Innovations Limited Recycling of lead- and tin-based materials
CN112534071B (en) * 2018-08-03 2023-09-22 帝国大学创新有限公司 Recovery of lead and tin materials
GB2586582A (en) * 2019-08-12 2021-03-03 Aeg Holdings Ltd Desulfurisation of lead-containing waste

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