GB2097774A - Process for treating sulphated lead compounds for recovering metallic lead and a high-purity sulphate - Google Patents

Process for treating sulphated lead compounds for recovering metallic lead and a high-purity sulphate Download PDF

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Publication number
GB2097774A
GB2097774A GB8211634A GB8211634A GB2097774A GB 2097774 A GB2097774 A GB 2097774A GB 8211634 A GB8211634 A GB 8211634A GB 8211634 A GB8211634 A GB 8211634A GB 2097774 A GB2097774 A GB 2097774A
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Prior art keywords
lead
sulphated
sulphate
sodium sulphate
crystallization
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GB2097774B (en
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TONOLLI COSTRUZIONI SpA
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TONOLLI COSTRUZIONI SpA
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • C22B13/045Recovery from waste materials
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)

Abstract

The process for treating sulphated lead compounds, more particularly those coming from exhausted storage batteries, comprises the steps of subjecting said sulphated compounds to leaching (12) with sodium carbonate in aqueous solution, collecting on a filter (15) the lead carbonate thus obtained from the sodium sulphate which is left dissolved, subjecting the lead carbonate to reduction (18) to metallic lead, separating the sodium sulphate by crystallization (22) from the filtrates (21) and recycling the mother liquors (23) of crystallization to the leaching stage (12). <IMAGE>

Description

SPECIFICATION Process for treating sulphate lead compounds for recovering metallic lead and a high-purity sulphate and an installation therefor This invention relates to a process for treating sulphated lead compounds for recovering metallic lead therefrom and, concurrently therewith, a high-purity sulphate, and an installation for performing said process.
The process to be described hereinafter is particularly suited to the treatment of sulphated lead compounds coming from acidic storage batteries with lead electrodes, which are exhausted ("electrodic pastes").
Many a process is known for recovering metallic lead from the "exhausted pastes" and from the sludges of the exhausted batteries; for example, pyrometallurgical processes are fairly known, in which the sulphated lead derivatives, mostly lead sulphate and lead sulphide, are reduced to metallic lead thermally. Serious objections against such processes are, on the one hand, the necessity of using reagents, such as iron and pyrite ashes, or slag forming compounds, such as soda or lime, at high temperatures, and, on the other hand, the fact that a high percentage of the sulphur which is contained in the starting materials is converted into noxious sulphurous gases which, if discharged into the atmosphere, originate ecological damages.It is thus imperative to provide to install purification systems in which the exhausted sulphurous gases ae subjected to scrubbing, for example with alkaline solutions, based on lime or ammoniacal solutions. It is apparent that this is a serious source of expenditures due to the first and running costs of such purification systems, so that this technology is exposed to heavy limitations.
For the same purposes as referred to above, are known, on the other hand, hydrometallurgical processes, such as those disclosed by the US Patents 3883348 and 4 118 219: these patients describe processes in which the materials which contain lead sulphate are treated with a solution of ammonium carbonate to give lead carbonate and ammonium sulphate, the latter beng recovered for being used as a fertilizer. Typical drawbacks of such processes are, however, the formation of ammoniacal gases and thus the processing conditions are hazardous and the necessity is felt of having specially designed systems available for concentrating the ammonium sulphate solutions and recovering the reactants, so that such processes are economically objectionable, also.
The RI 8123 of the Bureau of Mines (US Department of the Interior) describes the use of calcium hydroxide for converting lead sulphate into lead hydroxide. Concurrently, insoluble calcium sulphate is formed so that it becomes necessary to carry out a reducing melting of the mixture thus obtained in the presence of a large amount of "flux" such as a mixture of sodium chloride and potassium chloride.
Although the temperature at which such a reduction is low, the great mass of substances to be melted makes the process of doubtful acceptance from the economical standpoint.
Moreover, additional treatments are required to recover the fluxes.
The British Patent 1 535 025 discloses the dissolution of a "spent paste" which contains lead oxides and sulphates into an alkaline electrolyte, in the presence of sucrose so as to form a complex with lead, the solution thus obtained being then electrolyzed with insoluble anodes to recover metallic lead.
Also this process is both intricate and economically objectionable.
The US Patent 4 018 567 relates to an appartus which is rather intricate and is intended for the separation of the several component parts of acidic lead storage batteries.
In order to form, together with the finer particles of the active mass of the storage battery the thick medium which is required for making the lighter component parts, such as the separators and the casings, buoyant, while sinking the metallic component parts, such as bridge-poles and grids, the British Patent uses a solution of sodium carbonate.The Patent substantially discloses an intricate device for hydraulically and mechanically separating the several component parts involved, but does not give any adequate suggestions as to the procedure for making the recovery system for the several components economically advantageous: this could be done by a system which, in addition to a satisfactory recovery of the metal, would concurrently provide a complete and advantageous recovery of the sulphated compounds, that which would also prevent the ecological damage due to their scattering in the environment.
It can thus be appreciated that the processes as adopted heretofore for recovering metallic lead from its sulphated compounds involve problems which are predominantly health-hazard problems and economic disadvantage problems due to the processing conditions.
This invention has as its aim to solve the problems encountered with the processes of the prior art in this field. To achieve this objective the invention suggests a process for treating sulphated lead compounds, more particularly those coming from spent storage batteries, to recover both metallic lead and a high-purity sulphate, the process in question being characterized in that it comprises the steps of subjecting said sulphated compounds to leaching with sodium carbonate in aqueous solution, collecting on a filter the lead carbo nate precipitate thus obtained from the sodium sulphate which is left dissolved, subjecting the lead carbonate to reduction to metallic lead, separating the sodium sulphate by crystallization from the filtrates and recycling the crystallization mother liquors to the leaching stage.
The invention has, moreover, the object of providing an installation for performing the process referred to above, said installation substantially comprisng a reactor for carrying out the leaching of said sulphated lead compounds with sodium carbonate, means for feeding the reactants to the reactor, means for carrying out the filtration of the liquor exiting the reactor, a kiln for the thermal reduction of lead carbonate to give metallic lead, crystallization vats for separating the sodium sulphate from the filtrates and means for recycling the crystallization mother liquors to said reactor.
In order that the features and the advantages of the invention may be better understood, an example of practical performance of the process will be described hereinafter with reference to the accompanying drawing, which is a flow diagram of the process according to the invention.
According to what is shown in the diagram, a "spent paste" of exhausted storage batteries, which mainly contains lead sulphate, is charged at 11 into a reactor 12, for example a vat having heating and stirring means, which is also fed at 1 3 and 14 with an aqueous solution of Na2CO3 of medium strength. The "spent paste charged at 1 2 is obtained by separating the paste from the remaining component parts of the storage batteries by any appropriate method, for example as disclosed in the US Patents 3 456 886 and 3 614003.
In the reactor 12, which is maintained at a temperature between 30iC and 40 C with stirring for about one hour, the leaching stage is carried out, so that a double-exchange reaction takes place between the reacting salts, the result being the formation of lead carbonate in the form of an insoluble precipitate, and the formation of sodium sulphate which is extremely soluble in hot water and which thus remains dissolved therein. Once the reaction has been completed, the mixture thus obtained is fed to a filtration stage 15, such as a filter-press, to separate the precipitate from the solution. At the exit from this stage, there is obtained at 16, a solid which contains the derivatives, mainly lead carry nate, of the lead charge coming from 11.The solids are dried at 1 7 and fed at 1 8 to a stage of reduction, in a kiln to which coal is fed at 1 9 in the necessary amount (roughly 4% of the solids by weight).
From the reduction kiln, which is maintained at about 900C for one hour, raw metallic lead is drawn at 20. The filtrate 21, coming from the filtration stage 15, contains the as-produced sodium sulphate and the unreacted sodium carbonate from the leaching stage. The filtrate is collected in crystallization vats 22, wherein, by merely allowing the liquor to cool at room temperature, crystals of decahydrous sodium sulphate can grow. On completion of crystallization, the mother liquors 23 exiting 22 are recycled ta the reactor 1 2 for the subsequent step.
The crystals of sodium sulphate coming from the vats 22 are strained by centrifugation at 24, collected at 25 and subjected at 26 to drying in a low-temperature air-stream to give a high-purity anhydrous sodium sulphate which can be used for enamel coatings or glass mills directly and without requiring any further purification steps.
The process now described permits to convert the starting sulphated lead compounds into two recovered products having a high quality, such as raw metallic lead and pure anhydrous sodium sulphate, without being affected by any of the difficulties discussed above relatively to the prior art in this field.
The virtually total conversion of the charged lead into its non-sulphated compounds, mainly PbC03, permits to carry out a kiln reduction with times which are much shorter and at temperatures which are much lower than those adopted in the hitherto conventional processes of reduction of lead sulphate (or sulphide), and, above all, no fluxes or slagformers are required.
In the process according to this invention, it can be affirmed, when comparing it with the conventional pyrometallurgical procedures, that the potential out-put of the reduction kiln is improved by about 15%, the duration of the refractory liners of the kiln is extended by about 60%, the formation of fumes and slags is reduced by about 65%, the lead losses by scattering in the fumes and slags is reduced by about 50%, and finally, the power consumption is reduced by about 30%.
Above all, the process according to this invention, by providing for the total conversion of the sulphated lead compounds into lead carbonate prior to the reduction stage, prevents, in the latter stage, the emission of sulphurous gases, which, conversely, was invariably experienced in all those processes in which sulphated lead compounds were reduced. The starting sulphur, not only is no more scattered in the atmosphere in the form of noxious gases, but, conversely, is converted, in its turn, into a high-purity compound, that is sodium sulphate, the commercial value of which can be estimated to be such as to balance the processing costs for the added reactants.
An additional, considerable advantage afforded by the process of the invention is, as has been found, the circumstance that the sodium sulphate exiting the processing run, inasmuch as it crystallizes with 10 mols of water per mol of salt, considerably reduces the amount of water in play, whereby the recycling of the mother liquors of the process is facilitated and the possibility of any water pollution in the environment of the installation is drastically reduced.
It can thus be affirmed that the process according to this invention permits that the lead contained in sulphated lead residues may be recovered with a minimum loss of metal, a maximum economical efficiency and a substantial reduction of any risk of pollution of the enviroment.
The present invention thus affords a clean technology which is adapted to the treatment of all the sulphated compounds of lead. The process described herein can profitably be adopted, not only to the treatment of spent pastes and sludges from exhausted lead storage batteries to which it is particularly adapted, but also to the treatment of sulphurcontaining lead fumes and ores, after an appropriate sulphation of the materials to be processed.
It is apparent that the practical embodiment described herein must be construed as an example only inasmuch as a number of modifications can be adopted within the scope of the invention by anyone skilled in the art both in connection with the processing run and the installation for carrying it out, without thereby departing from the scope of the invention.

Claims (10)

1. A process for treating sulphated lead compounds for recovering metallic lead and a high-purity sulphate, characterized in that it comprises the steps of subjecting said sulphated compounds to leaching with an aqueous solution of sodium carbonate, collecting on a filter the lead carbonate precipitate thus obtained to separate it from the sodium sulphate being left dissolved, subjecting to reduction the lead carbonate to metallic lead, separating the sodium sulphate by crystallization from the filtrates, and recycling the crystallization mother liquors to the leaching stage.
2. A process according to Claim 1, characterized in that said reduction stage is carried out thermally, in the presence of coal at a temperature below 1 000 C.
3. A process according to Claim 1, characterized in that said crystallization stage is carried out by cooling said solution to give crystals of decahydrous sodium sulphate.
4. A process according to Claim 3, characterized in that said crystals separated from the mother liquors are subjected to drying to give anhydrous sodium sulphate to be sent to storage.
5. An installation for carrying out the process claimed in any of the preceding Claims substantially comprising a reactor for carrying out a leaching of said sulphated lead compounds with sodium carbonate, means for feeding the reactants to said reactor, means for carrying out the filtration of the solution exiting the reactor, a kiln for the thermal reduction of lead carbonate to give metallic lead, crystallization vats for separating sodium sulphate in crystals from the mother liquors of said filtration and means for recycling the mother liquors separated from said crystals to said reactor.
6. An installation according to Claim 5, characterized in that said filtration means consist of a filter-press.
7. An installation according to Claim 5, characterized in that it comprises a centrifuge for separating the sodium sulphate from the crystallization mother liquors.
8. An installation according to Claim 5, characterized in that it comprises devices for drying the crystals of hydrous sodium sulphate as obtained in said crystallization stage.
9. A process for treating sulphated lead compounds for recovering metallic lead and a high-purity sulphate substantially as hereinbefore described with reference to the accompanying drawing.
10. An installation for treating sulphated lead compounds for recovering metallic lead and a high-purity sulphate substantially as hereinbefore described with reference to the accompanying drawing.
GB8211634A 1981-04-29 1982-04-22 Process for treating sulphated lead compounds for recovering metallic lead and a high-purity sulphate Expired GB2097774B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT2144781A IT1136589B (en) 1981-04-29 1981-04-29 PROCEDURE FOR THE TREATMENT OF LEAD SULPHATE COMPOUNDS TO RECOVER METALLIC LEAD AND A HIGH-PURITY SULPHATE, AND PLANT FOR ITS REALIZATION

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GB2097774A true GB2097774A (en) 1982-11-10
GB2097774B GB2097774B (en) 1985-03-06

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GB8211634A Expired GB2097774B (en) 1981-04-29 1982-04-22 Process for treating sulphated lead compounds for recovering metallic lead and a high-purity sulphate

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BR (1) BR8202453A (en)
CA (1) CA1190401A (en)
DE (1) DE3215592A1 (en)
ES (1) ES511763A0 (en)
FR (1) FR2504940A1 (en)
GB (1) GB2097774B (en)
IT (1) IT1136589B (en)
YU (1) YU88682A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2592662A1 (en) * 1986-01-09 1987-07-10 Tecneco Spa PROCESS FOR RECOVERING THE CONSTITUENTS OF LEAD BATTERIES

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3612491A1 (en) * 1986-04-14 1987-10-15 Preussag Ag Metall Process for recovering lead from oxidic or oxidic/sulphatic secondary precursor materials

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1587623A (en) * 1925-03-02 1926-06-08 Max E Zuckerman Process of reclaiming the constituents of lead battery plates
US2152242A (en) * 1935-08-10 1939-03-28 Leo P Curtin Recovery of lead values
US3892563A (en) * 1973-05-14 1975-07-01 Point Albert E Method and apparatus for separating the constituents of lead-acid storage batteries
US4269810A (en) * 1978-10-10 1981-05-26 Nl Industries, Inc. Method for desulfation of battery mud
FI63781B (en) * 1980-03-19 1983-04-29 Outokumpu Oy FOERFARANDE FOER AOTERVINNING AV VAERDEMETALLER UR FINMALEN PYIT

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2592662A1 (en) * 1986-01-09 1987-07-10 Tecneco Spa PROCESS FOR RECOVERING THE CONSTITUENTS OF LEAD BATTERIES

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YU88682A (en) 1985-03-20
CA1190401A (en) 1985-07-16
IT8121447A0 (en) 1981-04-29
BR8202453A (en) 1983-04-12
IT1136589B (en) 1986-09-03
ES8302111A1 (en) 1983-02-01
GB2097774B (en) 1985-03-06
FR2504940A1 (en) 1982-11-05
ES511763A0 (en) 1983-02-01
DE3215592A1 (en) 1982-11-18

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