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
  • H01M10/54—Reclaiming serviceable parts of waste accumulators
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B13/00—Obtaining lead
  • C22B13/04—Obtaining lead by wet processes
  • C22B13/045—Recovery from waste materials
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
  • C22B7/006—Wet processes
  • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/20—Recycling
• • 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

• Secondary lead is recovered from the electrode slime recovered from end-of-life lead-acid batteries using pyrometallurgical processes operating at high temperature and in the presence of iron to reduce the furnace operating temperature to approximately 1100 °C. These processes have a potentially high environmental impact, both as regards gaseous emissions and the large associated output of slag, which is classified as a hazardous material requiring disposal in special dumps . As far as gaseous emissions are concerned, the procedures adopted by lead recyclers make it possible to reduce and control these, although at a high cost, while the problem associated with the large output of associated slag persists. Conversion of the lead sulphate present in the electrode slime into carbonate through a "carbonatation" process is a technique which is well known among secondary lead producers.
• a method for virtually wholly desulphating the slime by reaction with an aqueous solution containing ammonium carbonate or alkali (sodium, ammonium, potassium) carbonates in addition to other substances which have the power to dissolve the insoluble lanarkite has now been found and is the subject of this invention.
• the treatment temperature may be between ambient temperature and the boiling point of the solution, preferably between 60 and 100°C.
• the ratio by weight between the water in the solution and the slime lies between 0.6 and 5, preferably between 0.7 and 1.2.
• the sodium carbonate present in the solution is the stoichiometric quantity appropriate for the sulphate levels present in the electrode slimes with an excess of between 0.01% and 10%.
• the sodium hydroxide is added in such a way that the carbonate/hydroxide ratio by weight lies between 6.4 and 5.5 so as to accelerate the desulphating reactions without plumbites being present in solution.
• the water/slime ratio may also be chosen in relation to the subsequent treatment separating the desulphated slime from the solution (normally by sedimentation, filtration and/or centrifuging) . This does not apply any constraint on desulphating.
• the water/slime/quantity of sodium carbonate ratio also depends on the subsequent treatment which it is intended to use to separate the sodium sulphate which forms as a result of the desulphating reaction described.
• the efficiency of lead recovery with reference to the weight of the non-desulphated dry slime was 71-72% in comparison with the maximum of 66% which can be obtained by known methods, while the maximum theoretical yield is 72-73%, depending on the composition of the slime.
• the amount of slag formed essentially depends on substances present in the slime
• lanarkite substances having the ability to dissolve lanarkite, such as : amines, amides, MEA (monoethanolamine) , DEA (diethanolamine) , TEA (triethanolamine) , tartaric acid and tartrates, citric acid and citrates, glycolic acid, gluconates, alkali and ammonium acetates, alkali and ammonium nitrates, ammonia, EDTA and other complexing agents, and with ammonium carbonate alone.
• amines, amides MEA (monoethanolamine) , DEA (diethanolamine) , TEA (triethanolamine) , tartaric acid and tartrates, citric acid and citrates, glycolic acid, gluconates, alkali and ammonium acetates, alkali and ammonium nitrates, ammonia, EDTA and other complexing agents, and with ammonium carbonate alone.
• 100 kg of electrode slimes were charged into a cylindrical mill reactor and suspended in a solution comprising 100 kg of water, 24 kg of 99% pure sodium carbonate and 3 kg of 99.5% pure sodium hydroxide.
• the suspension was heated to a temperature of 70 °C and held at that temperature for 90 minutes.
• the solid part of the suspension was subjected to a strong compression and shearing force through rotating brushes brushing against the inside walls of the reactor.
• the solid part of the suspension was separated out from the suspension and on analysis was found to have a total sulphur content of less than 0.06%.
• 100 kg of electrode slime was charged into a cylindrical reactor with a paddle stirrer and suspended in a solution comprising 100 kg of water, 24 kg of 99% pure sodium carbonate and 8 kg of 99.5% pure sodium hydroxide.
• the suspension was heated to a temperature of 70 °C and held at that temperature for 90 minutes. Again in this case the grinding action was applied throughout the duration of the test.
• the solid part of the suspension was separated out from the and on analysis was found to have a total sulphur content of less than 0.04%.
• 100 kg of electrode slime was charged into the same cylindrical reactor as in example no. 1 and suspended in a solution comprising 100 kg of water, 24 kg of 99% pure sodium carbonate and 6 kg of monoethanolamine.
• the suspension was heated to a temperature of 70 °C and held at that temperature for 90 minutes. Again in this case the grinding action was maintained throughout the duration of the test.
• the solid part of the suspension was separated out and on analysis was found to have a total sulphur content of less than 0.07%.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Mechanical Engineering (AREA)
• Organic Chemistry (AREA)
• Metallurgy (AREA)
• Materials Engineering (AREA)
• Environmental & Geological Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Geology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Processing Of Solid Wastes (AREA)
• Secondary Cells (AREA)

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• 2004
  • 2004-07-12 CN CNA2004800250660A patent/CN1846005A/zh active Pending
  • 2004-07-12 WO PCT/IB2004/002285 patent/WO2005007904A1/en not_active Application Discontinuation
  • 2004-07-12 US US10/564,989 patent/US20070028720A1/en not_active Abandoned
  • 2004-07-12 EP EP20040743947 patent/EP1656463A1/en not_active Withdrawn

Non-Patent Citations (2)

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