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GB2258081A - Working up waste active-mass of consumed, broken accumulator plates deriving from rubbish-shoots into active-mass - Google Patents

Working up waste active-mass of consumed, broken accumulator plates deriving from rubbish-shoots into active-mass Download PDF

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Publication number
GB2258081A
GB2258081A GB9122628A GB9122628A GB2258081A GB 2258081 A GB2258081 A GB 2258081A GB 9122628 A GB9122628 A GB 9122628A GB 9122628 A GB9122628 A GB 9122628A GB 2258081 A GB2258081 A GB 2258081A
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GB
United Kingdom
Prior art keywords
mass
active
positive
heat
negative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB9122628A
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GB2258081B (en
GB9122628D0 (en
Inventor
Jozsef Keri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akkumulator Es Szarazelemgyar
Original Assignee
Akkumulator Es Szarazelemgyar
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB919115851A external-priority patent/GB9115851D0/en
Priority claimed from GB919121867A external-priority patent/GB9121867D0/en
Application filed by Akkumulator Es Szarazelemgyar filed Critical Akkumulator Es Szarazelemgyar
Publication of GB9122628D0 publication Critical patent/GB9122628D0/en
Publication of GB2258081A publication Critical patent/GB2258081A/en
Application granted granted Critical
Publication of GB2258081B publication Critical patent/GB2258081B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The waste active-masses removed from positive and negative plates are deacidified, washed with water, air dried, and subject to: a) heat-treatment at 500 to 700 DEG C for 8 to 60 minutes, then either ground or fed into a lead-powder mill in an amount at most 80 % by mass, calculated on the mass of the lead charged into the mill, and in both cases ground to an average particle size of less than 60 mu , or b) to grinding eg. to an average particle size of less than 60 mu , then subjected to a heat-treatment at 500 to 700 DEG C for 8 to 60 minutes, then from the thus-obtained material positive or negative active-mass is prepared when positive or negative active-mass was used as starting material, or negative active-mass is prepared when a mixture of positive and negative active-masses was used as starting material.

Description

PROCESS FOR WORKING UP WASTE ACTIVE-MASS OF CONSUMED, BROKEN ACCIJIULATOR PLATES DERIVING FROM RUBBISH-SHOOTS INTO ACTIVE-MASS Technical field The invention relates to a process for working-up waste active-mass of industrially operated consumed, broken accumulator plates, deriving from rubbish-shoots, into active-mass, wherein the waste active-masses removed from positive and negative plates are deacidified, washed with water, separately stored and then subjected to heat-treatment.
Background art The starting material for the production of active-mass is lead powder. Lead powder is prepared from lead, e.g. in a Barton mill commonly known in the industry, and in the course of milling, depending on the grinding conditions, lead oxide is also formed in different ratios.
The powder thus obtained is subjected to sulfuric acid/phoshoric acid treatment, depending on whether positive or negative active-mass is to be prepared, and additives, e.g.
sulfuric acid, barium sulfate, carbon black, are mixed to the product thus obtained. The resulting crude active-mass is spread onto electrodes of grid structure with the aid of a spreading machine. Then further operations are carried out on the mass thus applied onto the plates, e.g. pre-drying and aging. Finally the plates are placed into containers, wherein optionally the appropriate polarities are bound together, then the containers are filled with an acid and then closed.
In the accumulator production a certain amount of defective product is also produced, the accumulators are consumed during operation, they become unserviceable and sooner or later they are deposited in rubbish-shoots.
Therefore, the need for the reprocessing of unserviceable accumulators, especially of their most expensive and poisonous lead plates and masses, and the recycling of the same into the current production, exists for a long time. According to the most wide-spread method the accumulators are dismantled, washed, etc.
and subjected to metallurgical treatment, i.e. the lead alloy of the plate grid is melted, then a grid is formed from the melt.
Several processes are known for the re-use of the negative active-mass content of waste plates. According to US patent specification No. 4,009,833 the separated active-mass is recycled into the mixing machines. This process is more economic than the multi step chemical method when the active-mass is separated into its components by a wet chemical method but this method can be used only for the working up of negative activemass waste.
The common disadvantages of the known processes are the high energy- and water demand, low efficacy, health hazard and enviroment pollution.
In the course of production, wastes are also formed e.g.
when spreading the active-mass onto the grid, while drying and during formation of the plates, etc. The working up of the said waste is described in Hungarian patent specification No. 201,179.
The aim of our experiments and examinations was to find a simple process for the recycling of waste positive and negative active-masses separated from the consumed, industrially operated, broken accumulator plates deriving from rubbish-shoots, i.e. not from the factory, into the active-mass production in a simple way, without causing any deterioration in quality of the accumulators being the end-products of the process.
The invention is based on the recognition that the above aim can be achieved if the negative and positive active-masses deriving from consumed, broken, unserviceable accumulators of rubbish-shoots are washed acid-free, appropriately ground and subjected to a special heat-treatment. The quality of the accumulators assembled with the thus-obtained active-mass is equal to that of accumulators assembled with fresh active-".ass.
The invention is based on the further recognition that the mixture of waste positive and negative active-masses can be worked up into negative active-mass of good quality. This recognition is surprising as it overcomes a technical prejudice.
Namely, formerly it was an accepted view of persons skilled in the art that if production-refuse active-mass is used as starting material, negative active-mass of suitable quality can be prepared only from separately stored and treated negative activemass waste (Hungarian patent specification No. 201,179).
Summary of the invention Thus, the invention relates to a process for working up the waste active-mass of industrially operated consumed, broken accumulator plates, deriving from rubbish-shoots, into activemass, wherein the waste active-masses removed from the positive and negative plates are deacidified, washed with water, separately stored under air-dry conditions and then subjected to heat-treatment.
Detailed description of the invention According to the invention the air-dry positive or negative active-mass or the mixture thereof is subjected a) to heat-treatment at a temperature of 500 to 70000, preferably at 650 to 68000, more preferably at 660 to 67500, for 8 to 60 minutes, then either ground in a manner known per se or fed into a lead-powder mill in an amount of at most 80 % by mass, calculated on the mass of the lead charged into the mill, and in both cases ground to an average particle size of less than 60 /u, or b) to grinding in a manner known per se, preferably to an average particle size of less than 60 /u, then subjected to a heat-treatment at a temperature of 500 to 70000, preferably at 650 to 68000, more preferably at 660 to 67500, for 8 to 60 minutes, then from the thus-obtained material positive or negative active-mass is prepared when positive or negative active-mass was used as starting material, or negative active-mass is prepared when a mixture of positive and negative active-masses was used as starting material.
The main advantages of the process of the invention are as follows: a) The complete re-processing of waste accumulators deriving from rubbish-shoots is possible. After the mechanical dismantling, deacidifying and washing of the unserviceable accumulators, the total amount of the active-masses of the plates can be recycled into the accumulator production. As the plates and their masses are the most expensive components of the accumulators, the process is very economical.
b) The material of the waste plates is re-used in the accumulator production itself and not in an other industry. Thus, the amount of fresh lead required for the accumulator production is reduced, whereby the economy of the production is further enhanced.
c) The pollution caused by the storage of lead or lead compounds, being extremely harmful to the enviroment, is considerably reduced or fully eliminated.
The invention is further illustrated by the following non-limiting examples.
Example 1 Air-dry positive active-mass deriving from rubbish-shoots is heat-treated at a temperature of 670 to 6800C for 45 minutes in a closed apparatus, then fed into a powder mill in an amount of 25 % by mass, calculated on the lead fed into the mill. The whole amount of material leaving the mill must fall through a 60 mesh screen. Then the material is mixed to 12 to 13 % by mass of ion-exchanged water, thereafter 10 % by mass of sulfuric acid (density: 1.3 kg/dm3), and then 2 % by mass of phosphoric acid are added under continuous stirring. Stirring is continued for 3 minutes, then the substance is removed from the mixer and after cooling the positive active-mass thus obtained is spread onto lead grids in a manner known per se. After spreading, the usual operations (aging, drying, etc.) are carried out.
Example 2 The waste negative active-mass is ground in a Barton mill, then subjected to heat-treatment at a temperature of 675 to 680 OC for 40 minutes. The heat-treated mass is fed into a powder mill in an amount of 75 % by mass, calculated on the lead fed into the mill. Thereafter the process of Example 1 is followed.
ExaTitle 3 The process of Example 1 is followed except that a waste active-mass mixture composed of about 4 parts by mass of negative and 1 part by mass of positive active-mass is used as starting material. In this way negative active-mass is obtained.
Table 1 summarizes the average of test results obtained by using accumulators prepared from the waste active-mass according to the invention and by the conventional method, respectively.
The capacity tests were carried out according to IEC 95-1 (1988), the test on resistance against overcharging and the cold starting tests were carried out according to Hungarian Standard No. 591-1977 and IEC 95-1 (1988), respectively.
Table 1 No. of cell 1 2 3 Amount of active mass g/Ah 7.6 7.7 7.6 Capacity, Ah 97.8 97.9 97.8 Res. ag. overch., min. 7,50" 7'54" Cold starting, min. 1'41" 1'40" Res. ag. overch. = Resistance against overcharging after 4 cycles Cell No. 1 = with the plates produced according to Examples 1 and 3 Cell No. 2 = with the plates produced according to Examples 2 and 3 Cell No. 3 = with the plates produced by the conventional process Table 1 clearly shows that there is no significant difference between the characteristic features of the accumulators prepared by using the active mass produced according to the invention and by the conventional method. This means that the use-value of the active-mass deriving from waste, consumed accumulators, worked up according to the invention, is equivalent to that of the fresh active-mass.
Example 4 One proceeds as described in Example 1 with the difference that the waste positive mass is heat treated at a temperature of 510 to 5200C for 60 minutes.
The obtained positive mass has practically the same characteristics as that prepared according to Example 1.

Claims (4)

1. A process for working up the waste active-mass of industrially operated consumed, broken accumulator plates, deriving from rubbish-shoots, into active mass, wherein the waste active-masses removed from positive and negative plates are deacidified, washed with water, separately stored under air-dry conditions and then subjected to heat-treatment, which comprises the steps of subjecting the air-dry positive or negative activemass or the mixture thereof a) to heat-treatment at a temperature of 500 to 7000C for 8 to 60 minutes, then either grinding the heat treated active-mass in a manner known ser se or feeding it into a lead-powder mill in an amount of at most 80 % by mass, calculated on the mass of the lead charged into the mill, and in both cases grinding to an average particle size of less than 60 /u, or b) to grinding in a manner known per se, preferably to an average particle size of less than 60 /u, then subjecting it to a heat-treatment at a temperature of 500 to 7000C for 8 to 60 minutes, then preparing from the thus-obtained material positive or negative active-mass when positive or negative active-mass was used as starting material, or preparing negative active-mass when a mixture of positive and negative active-masses was used as starting material.
2. A process as claimed in claim 1, which comprises carrying out the heat-treatment at a temperature of 650 to 6800C.
3. A process as claimed in claim 1, which comprises carrying out the heat-treatment at a temperature of 660 to 6750C.
4. A process for working up the waste active-mass of discarded spent accumulator plates, into usable active mass, wherein the waste active-mass removed from positive and negative plates are deacidified, washed with water, stored under air-dry conditions and their subjected to heat-treatment, which comprises the steps of subjecting the air-dry positive or negative activemass or a mixture thereof a) to heat-treatment at a temperature of 500 to 7000C for 8 to 60 minutes, then either grinding the heat treated active-mass in a manner known per se or feeding it into a lead-powder mill in an amount of at most 80 % by mass, calculated on the mass of the lead charged into the mill, and in both cases grinding to an average particle size of less than 60 /u, or b) to grinding in a manner known per se, preferably to an average particle size of less than 60 /u, then subjecting it to a heat-treatment at a temperature of 500 to 70000 for 8 to 60 minutes, then preparing from the thus-obtained material, positive or negative active-mass when positive or negative active-mass (respectively) was used as the starting material, or preparing negative active-mass when a mixture of positive and negative active-mass was used as the starting material.
GB9122628A 1991-07-23 1991-10-24 Process for working up waste active-mass of discarded spent accumulator plates into active-mass Expired - Fee Related GB2258081B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919115851A GB9115851D0 (en) 1991-07-23 1991-07-23 Process for working up waste active-mass of consumed,broken accumulator plates deriving from rubbish-shoots into active-mass
GB919121867A GB9121867D0 (en) 1991-10-15 1991-10-15 Process for working up waste active-mass of consumed,broken accumulator plates deriving from rubbish-shoots into active-mass

Publications (3)

Publication Number Publication Date
GB9122628D0 GB9122628D0 (en) 1991-12-04
GB2258081A true GB2258081A (en) 1993-01-27
GB2258081B GB2258081B (en) 1995-04-05

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GB9122628A Expired - Fee Related GB2258081B (en) 1991-07-23 1991-10-24 Process for working up waste active-mass of discarded spent accumulator plates into active-mass

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FR (1) FR2683950B1 (en)
GB (1) GB2258081B (en)
SE (2) SE9102232L (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0948076A1 (en) * 1998-03-10 1999-10-06 Sony Corporation Method for manufacturing electrode comprising recovery and reuse of active mass
US6033722A (en) * 1996-09-12 2000-03-07 Sony Corporation Method for manufacturing electrode

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1471640A (en) * 1975-01-08 1977-04-27 Liniger A Process for recovering lead from the active material of used batteries
GB1535025A (en) * 1976-05-14 1978-12-06 Foerderung Forschung Gmbh Recovery of lead from batteries
GB2023183A (en) * 1978-06-10 1979-12-28 V Ni Gor Metal I Tsvet Metal Processing Storage Battery Lead Scrap
US4384683A (en) * 1980-06-18 1983-05-24 Hazemag Dr. E. Andreas Gmbh & Co. Method of recovering lead and lead compounds from discarded lead storage batteries
GB2236013A (en) * 1989-08-16 1991-03-20 Akkumulator Es Szarazelemgyar Recycling waste lead accumulators

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH241086A (en) * 1944-04-25 1946-02-15 Milo Gerolamo Method for removing gases contained in electrical elements, in particular accumulators.

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1471640A (en) * 1975-01-08 1977-04-27 Liniger A Process for recovering lead from the active material of used batteries
GB1535025A (en) * 1976-05-14 1978-12-06 Foerderung Forschung Gmbh Recovery of lead from batteries
GB2023183A (en) * 1978-06-10 1979-12-28 V Ni Gor Metal I Tsvet Metal Processing Storage Battery Lead Scrap
US4384683A (en) * 1980-06-18 1983-05-24 Hazemag Dr. E. Andreas Gmbh & Co. Method of recovering lead and lead compounds from discarded lead storage batteries
GB2236013A (en) * 1989-08-16 1991-03-20 Akkumulator Es Szarazelemgyar Recycling waste lead accumulators

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6033722A (en) * 1996-09-12 2000-03-07 Sony Corporation Method for manufacturing electrode
EP0948076A1 (en) * 1998-03-10 1999-10-06 Sony Corporation Method for manufacturing electrode comprising recovery and reuse of active mass

Also Published As

Publication number Publication date
GB2258081B (en) 1995-04-05
FR2683950B1 (en) 1994-01-28
GB9122628D0 (en) 1991-12-04
SE9102232D0 (en) 1991-07-24
SE9103176D0 (en) 1991-10-30
FR2683950A1 (en) 1993-05-21
SE9102232L (en) 1993-01-25
SE9103176L (en) 1993-01-25

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PCNP Patent ceased through non-payment of renewal fee

Effective date: 19981024