WO2003025235A1 - Process for the recovery of lead from scrap batteries - Google Patents

Process for the recovery of lead from scrap batteries Download PDF

Info

Publication number
WO2003025235A1
WO2003025235A1 PCT/NL2002/000592 NL0200592W WO03025235A1 WO 2003025235 A1 WO2003025235 A1 WO 2003025235A1 NL 0200592 W NL0200592 W NL 0200592W WO 03025235 A1 WO03025235 A1 WO 03025235A1
Authority
WO
WIPO (PCT)
Prior art keywords
lead
subjected
precipitation step
biological
process according
Prior art date
Application number
PCT/NL2002/000592
Other languages
French (fr)
Inventor
Cees Jan Nico Buisman
Merijn Amilcare Picavet
Original Assignee
Paques B.V.
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
Application filed by Paques B.V. filed Critical Paques B.V.
Publication of WO2003025235A1 publication Critical patent/WO2003025235A1/en

Links

Classifications

    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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

Definitions

  • the invention relates to a process for the recovery of lead from battery paste wherein the battery paste is subjected to a first lead precipitation step at high alkalinity, wherein lead is partially precipitated and separated, the liquid residue thereof is subjected to a second lead precipitation step at lower alkalinity, wherein remaining soluble lead is precipitated and filtered off, and a sodium sulphate solution remains.
  • Scrap batteries are usually recycled in order to recover the lead.
  • the batteries are first subjected to a shredder, which releases spent battery acid and battery paste, still containing solid particles such as polypropylene and ebonite.
  • the spent battery acid is fed through a filter press.
  • the filtered spent battery acid contains about 14% sulphuric acid and is stored in the spent battery acid storage.
  • the battery paste obtained after shredding is screened to remove large solid particles.
  • Battery paste, containing lead sulphate, lead oxide, water and sulphuric acid remains, h the conventional process, the battery paste is then contacted with concentrated caustic soda up to a pH of about 11.5 to 12, which results in conversion of lead to insoluble lead hydroxide and to soluble lead plumbate.
  • Filtered spent battery acid is also introduced into this stage in order to be neutralised.
  • the resulting suspension is filtered and the filter cake is used for lead recovery.
  • the filtrate is neutralised to by the addition of filtered spent battery acid to precipitate dissolved lead as insoluble hydroxide.
  • the suspension thus obtained is filtered.
  • the filter cake is conducted to the lead recovery.
  • the filtrate is essentially a solution of sodium sulphate (about 75 g/1), which is evaporated and eventually produces crystalline sodium sulphate. It can be reused in the glass and detergent industry.
  • a conventional plant that recovers lead from scrap batteries may process about 10,000 tons of lead, about 4000 tonnes of sulphuric acid, and produces about 6000 tons of sodium sulphate.
  • the lead content of battery paste is typically around 200 g/1, and the sulphuric acid content is around 30 g/1 (3 wt.%).
  • the level of impurities is low: typical impurities include calcium (35 mg/1), iron (less than 10 mg/1), antimony (about 9 g/1), bismuth (140 mg/1) and silver (40 mg/1).
  • the sulphuric acid content of spent battery acid is typically around 150 g/1 (14 wt.%).
  • DE-A-3612491 discloses a process for recovering lead from battery scrap by first treating a scrap fraction with a recycled alkaline solution leading to a sulphate-containing solution and a lead-containing residue, and further desulphuring the lead-containing residue with caustic soda solution which, after being deleaded with carbon dioxide, is recycled. This process still requires large amounts of caustic soda, and energy.
  • US 6,117,209 discloses a hydrometallurgical process for separating tin and antimony from lead-containing alloys, by leaching tin from the metal mixture using sulphuric acid, desulphurising the detinned residue with sodium carbonate, and extracting lead from the desulphurised residue with an acid such as fmoroboric acid. This process is not well suited for the treatment of battery scrap.
  • a process has been developed that results in a significant reduction of caustic soda consumption, and of sodium sulphate production, and furthermore reduces the energy input.
  • the improved process involves a biological sulphate removal step resulting in the production of elemental sulphur and a carbonate-containing solution that can be resued int the precipitation of lead.
  • a paste filtration step is performed on the battery paste before the first lead precipitation step and results in a filter cake largely consisting of lead sulphate and other lead salts, and a filtrate consisting of dilute sulphuric acid (about 3 wt.%).
  • This filtration step can be performed e.g. with a filter press. It has the considerable advantage of lowering the sulphate load in the lead precipitation steps, and thus in reducing the amount of alkali required in the first lead precipitation step.
  • the sulphuric acid of the filtrate can be combined with the sulphate solution resulting from the second lead precipitation step. This combination is especially useful when the sulphate solution is biologically desulphurised.
  • the biological sulphate reduction step is performed on the sodium sulphate solution resulting from the second lead precipitation step.
  • sulphuric acid originating from spent battery acid after separation of the battery paste instead of being added to the first lead precipitation step, can be combined with the sulphate solution in order to be desulphurised.
  • the filtrate resulting from the paste filtration step can be treated together with the sulphate solution.
  • the sulphate solution, single or combined, is biologically reduced in an anaerobic reactor to produce sulphide.
  • the sulphide-containing solution issuing from the anaerobic reactor is then aerobically oxidised under controlled conditions to produce elemental sulphur, which is subsequently separated and reused, e.g.
  • the liquid remaining after the sulphur separation is a weakly alkaline solution that can be used, after concentration, for rendering the pH alkaline in the first lead precipitation step.
  • Biological reduction of sulphite and sulphate followed by biological oxidation of the resulting sulphide to elemental sulphur is known per se, see e.g. WO 91/16269, WO 92/17410 and WO 93/24416.
  • the sulphate solution that is subjected to the biological sulphate reduction can contain sulphate in any form. Even though it is referred to herein as sodium sulphate solution, it can also be another sulphate salt or a combination thereof with sulphuric acid.
  • the sulphate solution is preferably diluted by means of recycling liquid originating from the elemental sulphur removal. This results in a sulphide concentration of less than 800 mg sulphur per 1 to avoid intoxication of the anaerobic bacteria by an excessive sulphide concentration. This may imply a recycle ratio of between 10 and 25 (recycle volume vs. treated volume through the biological desulphurisation).
  • the sulphate reduction can be carried out in a conventional anaerobic reactor, having a liquid inlet, a liquid outlet and means for keeping the anaerobic biomass in the reactor.
  • An electron donor is usually necessary for providing the required reduction equivalents.
  • Organic compounds such as alcohols or carboxylic acids, especially ethanol or acetic acid, can be used, but preference is given to hydrogen as an electron donor.
  • a convenient type of bioreactor wherein hydrogen can be fed is a gaslift loop reactor, wherein a vertical circulation of the treated liquid is maintained. Surplus hydrogen issuing from the anaerobic reactor can be recycled.
  • the pH in the anaerobic reactor is preferably between 7 and 8.5.
  • any residual lead (or other heavy metals) in the sulphate solution will be precipitated as metal sulphide as a result of the reduction of sulphate to sulphide, and can be separated by filtration.
  • the capacity of the anaerobic reactor maybe such that about 3 to 30 kg of sulphide, especially about 8 kg is produced per m per day.
  • the controlled conditions in the sulphide oxidation include a limited oxygen supply, which is sufficient to convert sulphide to elemental sulphur, but which avoids excessive sulphate production.
  • the oxidation can be carried out in a conventional aerobic reactor having aeration means and the necessary inlets and outlets.
  • a useful type of aerobic reactor is a so-called Circox reactor, wherein the medium containing the aerobic biomass and the components to be oxidised are circulated vertically.
  • a process for improved biological oxidation of sulphide to produce elemental sulphur using such an aerobic reactor, optionally preceded by sulphate reduction, is described in WO 94/29227.
  • the capacity may be such that about 5 to 50 kg of S, especially about 10 kg is produced per m 3 per day.
  • the effluent of the aerobic reactor is subjected to solid/liquid separation, resulting in solid elemental sulphur being separated off and a desulphurised liquid.
  • the desulphurised liquid contains alkaline components such as sodium hydroxide, carbonate bicarbonate, at a sodium concentration of about 10-20 g/1, and will have a pH of between 8 and 11. Thus it can be considered as an alkali regeneration liquid. It is advantageously used as an alkalinising reagent in the first lead precipitation step, and it may advantageously be concentrated to a concentration of about 20 to 35 g/1, e.g. if an inexpensive heat source such as steam is available, before being introduced into the lead precipitation tank. The use of the biological regeneration liquid in lead regeneration results in precipitation of lead as lead carbonate.
  • Figure 1 shows the paste dewatering. Battery paste 1 is fed to paste filtration unit 2.
  • the filter cake is neutralised in stage 1 lead desulphurisation (lead separation) 3, and the lead precipitate is filtered off (not shown).
  • the filtrate is fed to stage 2 lead desulphurisation (lead separation) 4, and then filtered in filtration unit 5.
  • the remaining filtrate, essentially sodium sulphate, can be conducted to the biological treatment at 11.
  • the biologically desulphurised liquid returns at 20 and can be concentrated and then used for neutralising stage 1 lead desulphurisation.
  • Figure 2 shows the biological treatment comprising the influent line 11, anaerobic bioreactor 12, aerobic bioreactor 13, sulphur separator and return line 20.
  • the liquid recycle serves to adjust the sulphide concentration and pH in the anaerobic bioreactor and will have a flow of about 205 m 3 /h (recycle ratio of about 18).
  • Sulphate is reduced in a gaslift loop reactor (12) using hydrogen as the electron donor.
  • S ⁇ 9 4 + 4H 2 + H + ⁇ HS ⁇ + 4H 2 0 The gaslift loop reactor ensures a good mass transfer of hydrogen from the gas phase to the liquid phase under mild conditions. In this way biological sulphate reducing activity loss due to high shear stress is prevented.
  • Mixing in the reactor is provided by natural circulation in the reactor by creating a difference in density using a gas recycle.
  • gas is sparged into the riser of the reactor lowering the density locally.
  • the liquid will have a tendency to rise.
  • the liquid loses its gas and the local density will rise. Subsequently, the liquid flows into the downer where there is a downward flow.
  • the hydrogen needed is produced by steam reforming natural gas.
  • the product gas contains 80 vol.% H 2 , 15 vol.% CO 2 and 5 vol.% inert gas.
  • the gas feed amounts to 650 Nm 3 /h.
  • a gas circulation of 3860 Nm 3 /h takes care of the natural liquid circulation in the reactor.
  • To prevent the accumulation of inert gasses about 100 Nm 3 /h have to be bled out of the process. This gas is used in the steam reforming process.
  • addition of nutrients is needed. In this case sources of carbon, nitrogen and phosphate are needed. These are respectively acetate, urea and phosphoric acid.
  • Sulphide oxidation Sulphide is removed by oxidising it with oxygen to elemental sulphur using sulphide oxidising bacteria in an aerobic reactor:
  • this is an alkalinity-producing stream.
  • This step can be considered as the alkalinity regeneration step.
  • the aerobic reactor (13) is operated under oxygen limitation as to prevent complete oxidation to sulphate:
  • the elemental sulphur is subsequently removed using a tilted plate separator (TPS).
  • TPS tilted plate separator
  • the obtained liquid stream is then led to the concentration step through evaporation.
  • the evaporated stream will be an alkaline stream with an estimated sodium concentration of 23.5 g/1. Most of the sodium will be present as bicarbonate ( ⁇ CO 3 " ) and carbonate (CO 3 2_ ) salts.
  • ⁇ CO 3 " bicarbonate
  • CO 3 2_ carbonate

Abstract

A process for the treatment of battery paste originating from spent batteries, wherein the battery paste is subjected to a first lead precipitation step at high alkalinity to partially precipitate and separate the lead, the liquid residue thereof is subjected to a second lead precipitation step at lower alkalinity to precipitate and separate remaining lead, and a sodium sulphate solution remains, is improved according the invention. Thus, the battery paste can be subjected to a filtration step before said first lead precipitation step, wherein the solid fraction of the filtration step is subjected to the lead precipitation step. The sodium sulphate solution remaining after the second lead precipitation step is subjected to a biological sulphate reduction and then to a controlled biological sulphide oxidation step to produce elemental sulphur and a reusable alkaline solution.

Description

Process for the recovery of lead from scrap batteries
The invention relates to a process for the recovery of lead from battery paste wherein the battery paste is subjected to a first lead precipitation step at high alkalinity, wherein lead is partially precipitated and separated, the liquid residue thereof is subjected to a second lead precipitation step at lower alkalinity, wherein remaining soluble lead is precipitated and filtered off, and a sodium sulphate solution remains.
Background
Scrap batteries are usually recycled in order to recover the lead. The batteries are first subjected to a shredder, which releases spent battery acid and battery paste, still containing solid particles such as polypropylene and ebonite. The spent battery acid is fed through a filter press. The filtered spent battery acid contains about 14% sulphuric acid and is stored in the spent battery acid storage. The battery paste obtained after shredding is screened to remove large solid particles. Battery paste, containing lead sulphate, lead oxide, water and sulphuric acid, remains, h the conventional process, the battery paste is then contacted with concentrated caustic soda up to a pH of about 11.5 to 12, which results in conversion of lead to insoluble lead hydroxide and to soluble lead plumbate. Filtered spent battery acid is also introduced into this stage in order to be neutralised. The resulting suspension is filtered and the filter cake is used for lead recovery. The filtrate is neutralised to by the addition of filtered spent battery acid to precipitate dissolved lead as insoluble hydroxide. The suspension thus obtained is filtered. The filter cake is conducted to the lead recovery. The filtrate is essentially a solution of sodium sulphate (about 75 g/1), which is evaporated and eventually produces crystalline sodium sulphate. It can be reused in the glass and detergent industry.
A conventional plant that recovers lead from scrap batteries may process about 10,000 tons of lead, about 4000 tonnes of sulphuric acid, and produces about 6000 tons of sodium sulphate. The lead content of battery paste is typically around 200 g/1, and the sulphuric acid content is around 30 g/1 (3 wt.%). The level of impurities is low: typical impurities include calcium (35 mg/1), iron (less than 10 mg/1), antimony (about 9 g/1), bismuth (140 mg/1) and silver (40 mg/1). The sulphuric acid content of spent battery acid is typically around 150 g/1 (14 wt.%).
The conventional process of recovering lead from scrap batteries requires large amounts of caustic soda for neutralising the acid. Moreover, the demand for sodium sulphate is limited, and thus the economic value of residual sodium sulphate is low, especially when compared to its purification cost and energy input required for its concentration (30 GWh for concentrating 6000 tons of sodium sulphate).
DE-A-3612491 discloses a process for recovering lead from battery scrap by first treating a scrap fraction with a recycled alkaline solution leading to a sulphate-containing solution and a lead-containing residue, and further desulphuring the lead-containing residue with caustic soda solution which, after being deleaded with carbon dioxide, is recycled. This process still requires large amounts of caustic soda, and energy. US 6,117,209 discloses a hydrometallurgical process for separating tin and antimony from lead-containing alloys, by leaching tin from the metal mixture using sulphuric acid, desulphurising the detinned residue with sodium carbonate, and extracting lead from the desulphurised residue with an acid such as fmoroboric acid. This process is not well suited for the treatment of battery scrap.
Description of the invention
A process has been developed that results in a significant reduction of caustic soda consumption, and of sodium sulphate production, and furthermore reduces the energy input. The improved process involves a biological sulphate removal step resulting in the production of elemental sulphur and a carbonate-containing solution that can be resued int the precipitation of lead.
Preferably, a paste filtration step is performed on the battery paste before the first lead precipitation step and results in a filter cake largely consisting of lead sulphate and other lead salts, and a filtrate consisting of dilute sulphuric acid (about 3 wt.%). This filtration step can be performed e.g. with a filter press. It has the considerable advantage of lowering the sulphate load in the lead precipitation steps, and thus in reducing the amount of alkali required in the first lead precipitation step. The sulphuric acid of the filtrate can be combined with the sulphate solution resulting from the second lead precipitation step. This combination is especially useful when the sulphate solution is biologically desulphurised.
The biological sulphate reduction step is performed on the sodium sulphate solution resulting from the second lead precipitation step. Also, sulphuric acid originating from spent battery acid after separation of the battery paste, instead of being added to the first lead precipitation step, can be combined with the sulphate solution in order to be desulphurised. Likewise, the filtrate resulting from the paste filtration step can be treated together with the sulphate solution. The sulphate solution, single or combined, is biologically reduced in an anaerobic reactor to produce sulphide. The sulphide-containing solution issuing from the anaerobic reactor is then aerobically oxidised under controlled conditions to produce elemental sulphur, which is subsequently separated and reused, e.g. in the production of sulphuric acid. The liquid remaining after the sulphur separation is a weakly alkaline solution that can be used, after concentration, for rendering the pH alkaline in the first lead precipitation step. Biological reduction of sulphite and sulphate followed by biological oxidation of the resulting sulphide to elemental sulphur is known per se, see e.g. WO 91/16269, WO 92/17410 and WO 93/24416.
The sulphate solution that is subjected to the biological sulphate reduction can contain sulphate in any form. Even though it is referred to herein as sodium sulphate solution, it can also be another sulphate salt or a combination thereof with sulphuric acid. The sulphate solution is preferably diluted by means of recycling liquid originating from the elemental sulphur removal. This results in a sulphide concentration of less than 800 mg sulphur per 1 to avoid intoxication of the anaerobic bacteria by an excessive sulphide concentration. This may imply a recycle ratio of between 10 and 25 (recycle volume vs. treated volume through the biological desulphurisation).
The sulphate reduction can be carried out in a conventional anaerobic reactor, having a liquid inlet, a liquid outlet and means for keeping the anaerobic biomass in the reactor. An electron donor is usually necessary for providing the required reduction equivalents. Organic compounds such as alcohols or carboxylic acids, especially ethanol or acetic acid, can be used, but preference is given to hydrogen as an electron donor. A convenient type of bioreactor wherein hydrogen can be fed is a gaslift loop reactor, wherein a vertical circulation of the treated liquid is maintained. Surplus hydrogen issuing from the anaerobic reactor can be recycled. The pH in the anaerobic reactor is preferably between 7 and 8.5. Further details on the performance of the anaerobic sulphide reactor can be found in WO 91/16269 and related prior art cited above. Any residual lead (or other heavy metals) in the sulphate solution will be precipitated as metal sulphide as a result of the reduction of sulphate to sulphide, and can be separated by filtration. The capacity of the anaerobic reactor maybe such that about 3 to 30 kg of sulphide, especially about 8 kg is produced per m per day. The controlled conditions in the sulphide oxidation include a limited oxygen supply, which is sufficient to convert sulphide to elemental sulphur, but which avoids excessive sulphate production. The oxidation can be carried out in a conventional aerobic reactor having aeration means and the necessary inlets and outlets. A useful type of aerobic reactor is a so-called Circox reactor, wherein the medium containing the aerobic biomass and the components to be oxidised are circulated vertically. A process for improved biological oxidation of sulphide to produce elemental sulphur using such an aerobic reactor, optionally preceded by sulphate reduction, is described in WO 94/29227. The capacity may be such that about 5 to 50 kg of S, especially about 10 kg is produced per m3 per day.
The effluent of the aerobic reactor is subjected to solid/liquid separation, resulting in solid elemental sulphur being separated off and a desulphurised liquid. The desulphurised liquid contains alkaline components such as sodium hydroxide, carbonate bicarbonate, at a sodium concentration of about 10-20 g/1, and will have a pH of between 8 and 11. Thus it can be considered as an alkali regeneration liquid. It is advantageously used as an alkalinising reagent in the first lead precipitation step, and it may advantageously be concentrated to a concentration of about 20 to 35 g/1, e.g. if an inexpensive heat source such as steam is available, before being introduced into the lead precipitation tank. The use of the biological regeneration liquid in lead regeneration results in precipitation of lead as lead carbonate.
By combining the paste filtration step with biological desulphurisation and alkali regeneration, alkali is used much more efficiently, which reduced the required amounts of caustic soda. The process of the invention is further illustrated with reference to the accompanying figures. Figure 1 shows the paste dewatering. Battery paste 1 is fed to paste filtration unit 2.
The filter cake is neutralised in stage 1 lead desulphurisation (lead separation) 3, and the lead precipitate is filtered off (not shown). The filtrate is fed to stage 2 lead desulphurisation (lead separation) 4, and then filtered in filtration unit 5. The remaining filtrate, essentially sodium sulphate, can be conducted to the biological treatment at 11. The biologically desulphurised liquid returns at 20 and can be concentrated and then used for neutralising stage 1 lead desulphurisation.
Figure 2 shows the biological treatment comprising the influent line 11, anaerobic bioreactor 12, aerobic bioreactor 13, sulphur separator and return line 20. The liquid recycle serves to adjust the sulphide concentration and pH in the anaerobic bioreactor and will have a flow of about 205 m3/h (recycle ratio of about 18).
Example: Biological treatment of sulphate from lead desulphurisation
Sulphate reduction
Sulphate is reduced in a gaslift loop reactor (12) using hydrogen as the electron donor. S<94 + 4H2 + H+ → HS~ + 4H20 The gaslift loop reactor ensures a good mass transfer of hydrogen from the gas phase to the liquid phase under mild conditions. In this way biological sulphate reducing activity loss due to high shear stress is prevented. Mixing in the reactor is provided by natural circulation in the reactor by creating a difference in density using a gas recycle. Thus, gas is sparged into the riser of the reactor lowering the density locally. The liquid will have a tendency to rise. In the upper part of the reactor the liquid loses its gas and the local density will rise. Subsequently, the liquid flows into the downer where there is a downward flow. The hydrogen needed is produced by steam reforming natural gas. Typically, the product gas contains 80 vol.% H2, 15 vol.% CO2 and 5 vol.% inert gas. The gas feed amounts to 650 Nm3/h. A gas circulation of 3860 Nm3/h takes care of the natural liquid circulation in the reactor. To prevent the accumulation of inert gasses, about 100 Nm3/h have to be bled out of the process. This gas is used in the steam reforming process. Next to hydrogen gas, addition of nutrients is needed. In this case sources of carbon, nitrogen and phosphate are needed. These are respectively acetate, urea and phosphoric acid.
Sulphide oxidation Sulphide is removed by oxidising it with oxygen to elemental sulphur using sulphide oxidising bacteria in an aerobic reactor:
Figure imgf000006_0001
As can be seen, this is an alkalinity-producing stream. This step can be considered as the alkalinity regeneration step.
The aerobic reactor (13) is operated under oxygen limitation as to prevent complete oxidation to sulphate:
HS~ + 202 → S04 2~ + H+
The elemental sulphur is subsequently removed using a tilted plate separator (TPS). The obtained liquid stream is then led to the concentration step through evaporation. The evaporated stream will be an alkaline stream with an estimated sodium concentration of 23.5 g/1. Most of the sodium will be present as bicarbonate (ΗCO3 ") and carbonate (CO3 2_) salts. For the oxidation of sulphide an air stream of 1450 Nm3/h is needed.

Claims

Claims
1. A process for the treatment of battery paste wherein the battery paste is subjected to a first lead precipitation step at high alkalinity to partially precipitate and separate the lead, the liquid residue thereof is subjected to a second lead precipitation step at lower alkalinity to precipitate and separate remaining lead, and a sodium sulphate solution remains, characterised in that the sodium sulphate solution remaining after the second lead precipitation step is subjected to a biological sulphate reduction and then to a controlled biological sulphide oxidation step to produce elemental sulphur.
2. A process according to claim 1, wherein the battery paste is subjected to a filtration step before said first lead precipitation step, wherein the solid fraction of the filtration step is subjected to the lead precipitation step.
3. A process according to claim 2, wherein said filtration step is performed by particle filtration using a filter press.
4. A process according to claim 2 or 3, wherein the filtrate from said filtration step is combined with said sodium sulphate solution and subjected to said biological sulphate reduction.
5. A process according to any one of claims 1-4, wherein the battery paste is obtained by separation of spent battery acid from crude spent battery acid by filtration and the filtered spent battery acid is combined with said sodium sulphate solution and subjected to said biological sulphate reduction.
6. A process according to any one of claims 1-5, wherein said biological sulphate reduction is performed using hydrogen, ethanol or acetic acid as an electron donor.
7. A process according to any one of claims 1-6, wherein the liquid effluent from said biological oxidation step is returned to the first lead precipitation step.
8. A process according to claim 1, wherein said liquid effluent is concentrated to a concentration between 20 and 30 g of salt (expressed as sodium) per 1.
9. A process according to claim 7 or 8, wherein a pH between 8 and 11 is maintained in the first lead precipitation step.
PCT/NL2002/000592 2001-09-17 2002-09-17 Process for the recovery of lead from scrap batteries WO2003025235A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01203523.4 2001-09-17
EP01203523 2001-09-17

Publications (1)

Publication Number Publication Date
WO2003025235A1 true WO2003025235A1 (en) 2003-03-27

Family

ID=8180939

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2002/000592 WO2003025235A1 (en) 2001-09-17 2002-09-17 Process for the recovery of lead from scrap batteries

Country Status (1)

Country Link
WO (1) WO2003025235A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010012058A2 (en) * 2008-07-28 2010-02-04 Almir Dos Santos Trindade Method for recycling used lead acid batteries electrolytic solution
US9533273B2 (en) 2014-06-20 2017-01-03 Johnson Controls Technology Company Systems and methods for isolating a particulate product when recycling lead from spent lead-acid batteries
US9670565B2 (en) 2014-06-20 2017-06-06 Johnson Controls Technology Company Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries
US10062933B2 (en) 2015-12-14 2018-08-28 Johnson Controls Technology Company Hydrometallurgical electrowinning of lead from spent lead-acid batteries
CN112501435A (en) * 2019-09-16 2021-03-16 河南永续再生资源有限公司 Lead plaster pretreatment process for waste batteries

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689253A (en) * 1970-08-27 1972-09-05 Minerals Technology Corp Reclaiming lead from storage batteries
US4118219A (en) * 1976-02-19 1978-10-03 Gould Inc. Process for recycling junk lead-acid batteries
DE3612491A1 (en) * 1986-04-14 1987-10-15 Preussag Ag Metall Process for recovering lead from oxidic or oxidic/sulphatic secondary precursor materials
WO1993024416A1 (en) * 1992-05-26 1993-12-09 Paques B.V. Process for removing sulphur compounds from water
US6117209A (en) * 1998-11-02 2000-09-12 Gnb Technologies, Inc. Hydrometallurgical process for treating alloys and drosses to recover the metal components

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689253A (en) * 1970-08-27 1972-09-05 Minerals Technology Corp Reclaiming lead from storage batteries
US4118219A (en) * 1976-02-19 1978-10-03 Gould Inc. Process for recycling junk lead-acid batteries
DE3612491A1 (en) * 1986-04-14 1987-10-15 Preussag Ag Metall Process for recovering lead from oxidic or oxidic/sulphatic secondary precursor materials
WO1993024416A1 (en) * 1992-05-26 1993-12-09 Paques B.V. Process for removing sulphur compounds from water
US6117209A (en) * 1998-11-02 2000-09-12 Gnb Technologies, Inc. Hydrometallurgical process for treating alloys and drosses to recover the metal components

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010012058A2 (en) * 2008-07-28 2010-02-04 Almir Dos Santos Trindade Method for recycling used lead acid batteries electrolytic solution
US20110129410A1 (en) * 2008-07-28 2011-06-02 Almir Dos Santos Trindade Method for recycling used lead acid batteries electrolytic solution
WO2010012058A3 (en) * 2008-07-28 2011-06-09 Almir Dos Santos Trindade Method for recycling used lead acid batteries electrolytic solution
US9751067B2 (en) 2014-06-20 2017-09-05 Johnson Controls Technology Company Methods for purifying and recycling lead from spent lead-acid batteries
US9555386B2 (en) 2014-06-20 2017-01-31 Johnson Controls Technology Company Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US9670565B2 (en) 2014-06-20 2017-06-06 Johnson Controls Technology Company Systems and methods for the hydrometallurgical recovery of lead from spent lead-acid batteries and the preparation of lead oxide for use in new lead-acid batteries
US11791505B2 (en) 2014-06-20 2023-10-17 Cps Technology Holdings Llc Methods for purifying and recycling lead from spent lead-acid batteries
US9757702B2 (en) 2014-06-20 2017-09-12 Johnson Controls Technology Company Systems and methods for purifying and recycling lead from spent lead-acid batteries
US9533273B2 (en) 2014-06-20 2017-01-03 Johnson Controls Technology Company Systems and methods for isolating a particulate product when recycling lead from spent lead-acid batteries
US10122052B2 (en) 2014-06-20 2018-11-06 Johnson Controls Technology Company Systems and methods for purifying and recycling lead from spent lead-acid batteries
US10403940B2 (en) 2014-06-20 2019-09-03 Cps Technology Holdings Llc Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US10777858B2 (en) 2014-06-20 2020-09-15 Cps Technology Holdings Llc Methods for purifying and recycling lead from spent lead-acid batteries
US11923518B2 (en) 2014-06-20 2024-03-05 Clarios Advanced Germany Gmbh & Co. KG Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling lead from spent lead-acid batteries
US11005129B2 (en) 2014-06-20 2021-05-11 Clarios Germany Gmbh & Co. Kgaa Systems and methods for closed-loop recycling of a liquid component of a leaching mixture when recycling 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
CN112501435A (en) * 2019-09-16 2021-03-16 河南永续再生资源有限公司 Lead plaster pretreatment process for waste batteries

Similar Documents

Publication Publication Date Title
US11634789B2 (en) Selective lithium extraction from brines
BG62290B1 (en) Hydrometallurgical metal extraction by means of a chloride
CA2808627C (en) Processing of manganous sulphate/dithionate liquors
PT2160480E (en) Cyanide process for precious metal recovery from a sulphide ore or concentrate or other sulphur containing feed material
WO1997029055A1 (en) Process for the treatment of water containing heavy metal ions
EA005464B1 (en) Method for recovering copper
CN102642953B (en) Treatment method for high-salinity heavy-metal-containing production sewage
PL205105B1 (en) Process for direct electrowinning of copper
EP3423613A1 (en) Sulfide recycling in manganese production
US5630931A (en) Process for the hydrometallurgical and electrochemical treatment of the active mass of exhausted lead batteries, to obtain electrolytic lead and elemental sulphur
AU665981B2 (en) Cyanide recycling process
US6852305B2 (en) Process for the production of hydrogen sulphide from elemental sulphur and use thereof in heavy metal recovery
US7285677B1 (en) System and method for recovering CTA residues and purifying/regenerating catalyst
CN101466855B (en) Nickel sulphide precipitation process
WO2003025235A1 (en) Process for the recovery of lead from scrap batteries
CA2349295C (en) Process for the production of hydrogen sulphide from elemental sulphur and use thereof in heavy metal recovery
NL1013590C2 (en) Method for the selective removal of metals from concentrated metallic streams.
JP3945216B2 (en) Waste acid gypsum manufacturing method
AU2003233283B2 (en) Chloride assisted hydrometallurgical extraction of metals
CN101224875A (en) Method for reclaiming sulfuric acid from vanadium-containing stone coal oxygen pressure acid drench
GB2163141A (en) Method for removing and recovering sulphur in elemental form from gases containing sulphur dioxide or sulphur dioxide and hydrogen sulphide
US5618507A (en) Process for removing SO2 from gases which contain it, with direct production of elemental sulfur
US1969567A (en) Process for the treatment of zinc sulphide ores
JP3647362B2 (en) Apparatus and method for automatically cleaning liquid after copper removal
JP3773672B2 (en) Copper electrolyte solution purification apparatus and method

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE ES FI GB GD GE GH HR HU ID IL IN IS JP KE KG KP KR LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NO NZ OM PH PL PT RU SD SE SG SI SK SL TJ TM TN TR TZ UA UG US UZ VC VN YU ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ UG ZM ZW AM AZ BY KG KZ RU TJ TM AT BE BG CH CY CZ DK EE ES FI FR GB GR IE IT LU MC PT SE SK TR BF BJ CF CG CI GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP