Guidelines for Environmentally Sound Management of Used Batteries in the Mediterranean Guidelines for Environmentally Sound Management of Used Lead Batteries in the Mediterranean Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Legal notice Copyright The designations employed and the presentation This publication may be reproduced in whole or in of the material in this document do not imply the part and in any form for educational or non-profit expression of any opinion whatsoever on the part purposes without special permission from the of UNEP/MAP Coordinating Unit concerning the copyright holder, provided acknowledgement legal status of any State, Territory, city or area, or of the source is made. UNEP/MAP Coordinating if its authorities, or concerning the delimitation of Unit would appreciate receiving a copy of any their frontiers or boundaries. publication that uses this publication as a source. This publication cannot be used for resale or for any other commercial purpose whatsoever without permission in writing for UNEP/MAP ISBN: 978-92-807-3520-8 Coordinating Unit. Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Preface This technical guide is focused and environmental hazard together with in implementing the relevant priority on the environmentally sound enhanced law enforcement. actions of the National Action Plans management (ESM) of lead batteries This technical guide provides adopted in the framework of Article and its ultimate objective is to provide background information and data on 5 and 15 of the LBS Protocol of the the Mediterranean countries with sources and amounts of produced used Barcelona Convention and its Strategic information in order to establish a proper lead batteries, an overview of available Action Programme SAP-MED. to prevent human standards, technical specification and health and environmental hazard. guidelines on the storage and treatment It has been developed by UNEP/MAP of batteries and accumulators as well as MED POL Programme in collaboration information on associated environmental with the Regional and health aspects. It also describes Centre in Bratislava in 2014, under the the collection, and storage, MedPartnership project1 and in the treatment and recovery of used lead framework of MAP Programme of Work batteries, as well as their transboundary 2014-2015. movement. Finally it explains potential sources of environmental contamination, The management of used lead batteries and discusses economic aspects of refers to the overall process of collection, environmentally sound management of transport, recovery and/or disposal used lead batteries. of used lead batteries, including the supervision of such operations. This guide was reviewed by an expert The system of environmental sound meeting and endorsed by the MAP Focal management of used lead batteries Points meeting in 2015. It is published can be successfully implemented only online in English and French as an effort when legislative rules are effective to support the Mediterranean countries and applicable, all or at least most of producers /importers of lead batteries are participating in the system, facilities for lead are available in appropriate distance (best of all in the 1. The Strategic Partnership for the Mediterranean Sea Large Marine Ecosystem (MedPartnership) is a collective effort country or in a not-very-far distance in of leading organizations (regional, international, nongovernmental, etc.) and countries sharing the Mediterranean Sea neighbouring countries), and effective towards the protection of the marine and coastal environment of the Mediterranean. The MedPartnership is being led state control to prevent human health by United Nations Environment Programme (UNEP) Mediterranean Action Plan (MAP) and the World Bank and is financially supported by the Global Environment Facility (GEF), and other donors, including the (EU) and all participating countries.

4 5 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Table of contents

DEFINITIONS 9 TREATMENT OF USED LEAD BATTERIES 38

DESCRIPTION OF A LEAD BATTERY 10 RECOVERY OF USED LEAD BATTERIES 41

ENVIRONMENTAL AND HEALTH ASPECTS 12 DISPOSAL OF USED LEAD BATTERIES 56 9.1. for hazardous 56 SOURCES OF LEAD BATTERIES, ESTIMATION OF 9.2. The underground long-term storage for hazardous wastes 60 AMOUNTS OF PRODUCED USED LEAD BATTERIES 14 9.3. Accepting waste for disposal 61

OVERVIEW OF AVAILABLE STANDARDS, TECHNICAL TRANSBOUNDARY MOVEMENT OF USED LEAD BATTERIES 62 SPECIFICATION AND GUIDELINES ON THE STORAGE AND 10.1. General requirements for “transport” / ADR 64 TREATMENT OF BATTERIES AND ACCUMULATORS 17 10.2. Special care for batteries and accumulators 5.1. European Union Legislative Framework 17 with a liquid electrolyte 67 5.2. Best Available Techniques Reference Documents of the European Commission 18 POTENTIAL SOURCES OF ENVIRONMENTAL CONTAMINATION 67 5.3. Basel Convention on the Control of Transboundary 11.1. Battery Breaking Process 67 Movements of Hazardous Wastes and Their Disposal 21 11.2. Lead Reduction Process 68 5.4. Guidelines on best available techniques and provisional 11.3. Lead Refining Process 70 guidance on best environmental practices of the 11.4. Bad examples of potential contamination of Stockholm Convention 21 the environment 71 General information on emissions from secondary lead smelters 21 ECONOMIC ASPECTS OF ENVIRONMENTALLY SOUND Emissions of PCDD/PCDF to air during the smelting process 22 MANAGEMENT OF USED LEAD BATTERIES 72

COLLECTION, TRANSPORT AND STORAGE OF USED CONCLUSIONS AND RECOMMENDATIONS 74 LEAD BATTERIES 23 6.1. General occupational health and safety recommendations LITERATURE 76 for workers during the and treatment of used lead batteries 24 6.2. Collection and sorting of used lead batteries 24 6.3. Transport of used lead batteries 28 6.4. Storage of used lead batteries 32

6 7 Definitions or in suitable containers. Treatment of used lead batteries - means Battery - any device that stores energy for recovery or disposal operations with used later use; common use of the word, “battery”, lead batteries, including preparation prior to however, is limited to an electrochemical recovery or disposal device that converts chemical energy into Recovery - means any operation the electricity, by use of a galvanic cell. principal result of which used lead batteries Galvanic cell - a device consisting of two serving a useful purpose by replacing other electrodes (an anode and a cathode) and an materials which would otherwise have been electrolyte solution; batteries may consist of used to fulfil a particular function, or waste one or more galvanic cells. being prepared to fulfil that function, in the Lead battery - the electrical accumulator plant or in the wider economy in which the active material of the positive Recycling - means any recovery operation plates is made up of lead compounds and by which used lead batteries materials are that of the negative plates is essentially lead, reprocessed into products, materials or the electrolyte being a dilute sulphuric acid substances whether for the original or other solution. purposes Used lead battery - the battery which is no Fractions of used lead batteries – material longer capable to be recharged or cannot parts and pieces produced from treatment retain its charge properly, its lifetime reaches of used lead batteries and relevant by- its end and it becomes a waste. processes of used lead batteries Management of used lead batteries - the Disposal - means any operation which is not overall process of collection, transport, recovery even where the operation has as a recovery and or disposal of used lead secondary consequence the reclamation of batteries, including the supervision of such substances or energy. operations. Separate collection - the gathering of used lead batteries, including the preliminary sorting and preliminary storage of used lead batteries for the purposes of transport to a treatment facility. Storage - placing of used lead batteries in the room of waste management or treatment facilities in sites with impermeable surfaces and suitable weatherproof covering

8 9 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Description of a lead from the anode to the cathode. The Positive and negative terminals: made separators. Plates of same polarity are battery electrons combine with the material in the of lead, and where the external electricity electrically connected. cathode through reduction and release a consumer devices are connected; The battery plates are constituted by A battery mainly consists of electrodes negatively charged metal – oxide ion. When Plugs: one for each battery element, where metallic lead structures, known as grids, (two plates, made from lead) placed in the anode is fully oxidised or the cathode distilled/deionised can be replaced covered by a lead dioxide paste, in the an electrolyte solution (sulphuric acid). is fully reduced, the chemical reaction will whenever needed and also to provide an case of the negative plates, or by a porous The metal in the anode oxidises releasing stop and the battery is considered to be escape route for gases formed in the cells; metallic lead paste, in the case of the negatively charged electrons and positively discharged. The schematic description of a Connectors: made of lead, that makes positive plates. The lead used in both charged metal ions. The electrons travel lead battery is shown in Figure 1. electrical contact between plates of same the plates may also contain several other polarity and also makes electrical contact chemical elements such as antimony, between separated elements; arsenic, bismuth, , , calcium, Cap and box: originally made of ebonite, , tin and sometimes other elements. but now more commonly made from either The plates manufacture process also or co-polymer; uses expander materials, such as barium Sulphuric acid solution: the electrolyte of sulphate, lampblack and lignin added in the battery; order to prevent the plate retraction during Element separators: usually a part of the use. Once prepared, the plates are dried, box and made of the same material provide cured and shaped ready to be assembled chemical and electrical isolation between into the battery elements. the electrical elements. They are connected manufactures produce in a serial layout in order to increase the final a full range of starter batteries for all types voltage of the battery; of vehicles using petrol and diesel engines. Plate separators: made of PVC or other The characteristic of lead acid batteries porous materials, avoid physical contact are large weight, relatively short shelf life between two contiguous plates but, at the without recharge, and a good ability to same time, allowing free movement of ions deliver high currents. Lead batteries are very in the electrolyte solution; adapted for uses requiring (occasional) high Negative plates: constituted by a metallic current draw, and where charging is regular lead grid covered by a lead dioxide (PbO2) (i.e. automotive). The lead battery has high paste; energy storage capacity and low cost. Positive plates: constituted by metallic lead plates; Battery element: a series of negative and positive plates placed consecutively and Fig. 1: Schemes of a lead battery and pictures with its labelling isolated between each other with plate (Author: Neil McNiven)

10 11 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Environmental and The sulphuric acid in a lead acid battery health aspects is highly corrosive and is potentially more harmful than acids used in other battery Used batteries pose a threat to our systems. Eye contact can cause permanent environment and should be managed blindness; swallowing damages internal properly. The toxic materials present in the organs that can lead to death. battery can cause harm to the environment and to human beings also. This is the reason why waste battery recycling should be done properly. The incorrect management of waste lead batteries cause danger to , soil and air, as well as to human health. Batteries are safe, but precaution applies when touching damaged cells and when handling lead acid systems that have access to lead and sulphuric acid. Lead batteries are labelled as hazardous material. Lead is a toxic metal that can enter the body by inhalation of lead dust or ingestion when touching the mouth with lead-contaminated Fig. 2: Major pathways of human lead intake1 hands. If leaked onto the ground, the acid and lead contaminate the soil There are many facilities which have is also recycled for further use; and become airborne when dry. implemented battery recycling as part Lead waste battery processing follows Exposure to lead causes a variety of health of their prevention efforts. The good environmental policy; effects, and affects children in particular. facility that makes the decision to implement The battery scrap recycling saves natural Lead is a metal with no known biological used battery recycling will help to protect resources. benefit to humans. Too much lead can the environment and insure the compliance The major use of lead in the world is in the damage various systems of the body with environmental laws. There are many form of lead acid batteries. Lead acid storage including the nervous and reproductive benefits of the lead battery scrap processing. batteries are an essential component of the systems and the kidneys, and it can cause Used battery recycling keeps all the automotive industry for which there are high blood pressure and anaemia. hazardous metals in one place; currently no electro-chemical, economic or There is no known safe blood lead The metals obtained in discharged environmentally acceptable alternatives. So concentration. But it is known that, as lead car battery processing are reused in this makes the used battery recycling more exposure increases, the range and severity manufacturing process to build more batteries; important. Lead recycling saves money, lead of symptoms and effects also increases.3 The (PP) from outer case of battery and most importantly, the environment.

12 13 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Sources of waste lead batteries, estimation of amounts of produced used lead batteries

Lead batteries are used in vehicles of all types. As the amount of vehicles is gradually increasing all around the world, the amount of used batteries is also growing (in Figure 3, 4 and 5 the examples of the European market for automotive batteries are shown).

Fig. 4: Aftermarket battery volume for EU Fig. 5: Aftermarket battery per (2011 – 2015, in k Units). 5 country in 2011.5

Another example is the consumption of lead households purchase more than 7.6 million acid batteries in Australia provided by the or 86,000 tonnes of lead acid batteries each Fig. 3: Vehicle Production Europe and the outlook 2011-2015 (in k units) for CARS, Australian Battery Recycling (ABRI) Initiative year, and dispose of more than 6.4 million or HCV - Heavy Commercial Vehicles and LCV - Light Commercial Vehicles, from 2010 [6]. In total, about 9.2 million lead 92,000 tonnes of them. Lead acid batteries Automotive Battery Committee, 2012 acid batteries are purchased and 7.8 million are most commonly used in cars, according reach the end of their useful life in Australia to both the Pollinate and the ABRI research every year. By weight, lead acid batteries (see Table 1). Car batteries make up 63 % of make up 91 %, or over 120,000 tonnes of the all lead acid batteries used in Australia. batteries disposed of in Australia. Australian

14 15 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Table 1: Lead acid battery use in Australian households reported by Overview of available equivalent to those set out in the EU Australian Battery Recycling Initiative in 2010 based on the survey.6 standards, technical Batteries Directive, including recycling specification and efficiencies. guidelines on the storage and treatment Article 12(2) and Annex III, Part A of the of batteries and EU Batteries Directive (2006/66/EC)9 set accumulators following requirements on waste battery treatment: 5.1. European Union Legislative Exclusively best available techniques are Framework to be used. The European Commission’s “Questions The minimum requirements set to be met and answers on the Batteries Directive” 8 include: provide an introduction to the requirements 1. Treatment shall, as a minimum, include which must be met by EU waste battery removal of all fluids and acids. Q1: Which of the following items do you have? industrial companies. In countries with treatment systems and to the requirements 2. Treatment and any storage, including Q2: Which of the following items had their lower living standard also individuals which must be met during export of waste temporary storage, at treatment facilities battery changed MOST recently? change car batteries by themselves and batteries: shall take place in sites with impermeable Base: Total sample Australians aged 14 – 64 households represent an important source surfaces and suitable weatherproof (September 2011, n = 1000) of used lead batteries. In European countries Does the EU Batteries Directive (2006/66/ covering or in suitable containers. The source of used lead batteries in the the amount of produced used lead batteries EC)9 lay down any requirements for Recycling processes shall achieve the country are mostly professional car services, per inhabitant and year is approximately treatment of waste batteries? following minimum recycling efficiencies: construction companies using internal 1.2 – 1.5 kg. In addition to levels of recycling efficiency, a) recycling of 65 % by average weight car maintenance, agricultural farms using A typical composition of lead – acid battery the Directive specifies how waste of lead-acid batteries and accumulators, internal car maintenance and some other scrap is given in Table 2 7. batteries are to be treated. The minimum including recycling of the lead content requirement is that fluids and acids must to the highest degree that is technically be removed. The Directive also describes feasible while avoiding excessive costs; Table 2: Composition of typical lead – acid automotive battery scrap 7 the conditions under which waste b) recycling of 75 % by average weight batteries must be treated and stored of -cadmium batteries and (Article 12(2) and Annex III, Part A). accumulators, including recycling of What requirements must be met if the cadmium content to the highest batteries are exported for recycling? degree that is technically feasible while When waste batteries are exported avoiding excessive costs; and outside the European Union, Member c) recycling of 50 % by average States must require sound evidence that weight of other waste batteries and the recycling takes place under conditions accumulators.

16 17 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

In Article 13 of the EU Batteries Directive Reference Documents on Best Available Table 4: Summary of the BREF on Best Available Techniques (2006/66/EC)9 it is recommended Techniques (BREFs) were prepared on the in the Non Ferrous Metals Industries 7, 11 that Member States shall encourage request of the European Commission. A The BREF on best available techniques in the Non Ferrous Metals Industries covers the the development of new recycling and dedicated BREF on waste battery treatment techniques for the production of both primary and secondary non-ferrous metals. The treatment technologies and does not exist. However, following BREFs production of 42 non-ferrous metals and the production of ferro alloys are addressed. that Member States shall encourage contain some specifications which are Ten groups of metals with similar production methods are dealt with in the document: treatment facilities to introduce certified relevant for waste battery treatment: • Copper and its alloys, Tin and Beryllium environmental management schemes (e.g. • and its alloys EMAS or ISO 14000). A) Reference Document on Best Available • , Lead, Cadmium, Antimony and Bismuth etc. 10 • Precious metals No further details on how to treat waste Techniques on Emissions from Storage • batteries and accumulators are provided by (for a summary of this BREF see Table 3). • Refractory metals, e.g. Chromium, Tungsten, Vanadium, Tantalium, Niobium, EU legislation9. B) Reference Document on Best Available Rhenium, Molybdenum • Ferro alloys, e.g. IronChromium, IronSilicon, IronManganese, SiliconManganese, Techniques in the Non Ferrous Metals IronTitanium, IronMolybdenum, IronVanadium, IronBoron 5.2. Best Available Techniques Industries, 11, 7 (for a summary of this BREF • Alkali and alkaline earth metals, Sodium, Potassium, , Strontium, Calcium, Reference Documents of the European see Table 4). Magnesium and Titanium Commission C) Best Available Techniques (BAT) • Nickel and • and graphite electrodes. The production of carbon and graphite anodes is In order to specify what the Best Available Reference Document for and included because of the production of anodes at some aluminium smelters as an Techniques for the respective sectors Production , 12 (for a summary of this integral part of the production process. and industrial processes are a number of BREF see Table 5). Table 5: Summary of the Best Available Techniques (BAT) Reference Document for Iron and Steel Production12 Table 3: Summary of the BREF on Emissions from Storage10 The BREF on Best Available Techniques for Iron and Steel Production covers the processes involved in the production of iron and steel in integrated works as well as the production The BREF on Emissions from Storage addresses the storage and the transfer/ of steel in electric arc furnace steelworks. The main operations covered are: handling of liquids, liquefied gases and solids, regardless of the sector or industry. It addresses emissions to air, soil and water. However, most attention is given to • Loading, unloading and handling of bulk raw materials emissions to air. Energy and noise are also addressed but to a lesser extent. • Blending and mixing of raw materials • Coke production Following storage methods for solids are addressed in particular: • Sintering and palletisation of iron ore • Heaps • Production of molten iron by a blast furnace route, including slag processing • Sacks and bulk bags • Production and refining of steel using the basic oxygen process, including upstream ladle de-sulphurisation, downstream ladle metallurgy and slag processing • Silos and bunkers • Production of steel by electric arc furnaces, including downstream ladle metallurgy • Packaged dangerous solids and slag processing • Containers and the storage of containers. • Continuous casting.

For the transfer and handling of solids, techniques such as mobile unloading Other downstream metal processing activities can be found in other BREF documents devices, grabs, dump pits, fill pipes, thrower belts, conveyors and feeders are (e.g. see BREF on Ferrous Metals Processing Industry [12] or BREF on Smitheries and described. In each case the emission sources are identified. Foundries Industry 14)

18 19 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

D) Reference Document on Best Available 5.3. Basel Convention on the Control from unintentional production 24. Techniques for the Waste Treatment of Transboundary Movements of Thermal process of used lead batteries in Industries 13 (for a summary of this BREF Hazardous Wastes and Their Disposal the metallurgical industry i.e. secondary see Table 6). Basel Convention on the Control of involves the production of Transboundary Movements of the lead and lead alloys, primarily from scrap Table 6: Summary of the BREF for the Waste Treatment Industries13 Hazardous Wastes and Their Disposal automobile batteries, and also from other regulates conditions for transboundary used lead sources (pipe, solder, drosses, The BREF for the Waste Treatment Industries covers the installations of a number shipment of hazardous wastes to protect lead sheathing). Production lead processes of waste (hazardous and non-hazardous) treatment processes, and deals with: environment of the developing countries include lead batteries scrap treatment, • Common waste treatment processes such as temporary waste storage, from the negative effects of inappropriate smelting and refining. Incomplete blending and hou, repackaging, waste reception, sampling, checking and waste disposal. The Secretariat of the combustion; high levels of oils, analysis, waste transfer and handling installations, and waste transfer stations Basel Convention has published several and other organic materials in feed; and • Biological waste treatment processes such as aerobic/anaerobic treatment guidelines, one of them dealing with temperatures between 250°C and 500°C processes and mechanical and biological treatment processes management of waste lead – acid batteries1. may all give rise to chemicals listed in • Physico- treatment processes of such as neutralisation, The guideline in detail describes applied Annex C of the Stockholm Convention. chromic acid and cyanide treatment, dewatering, filtration, harbour reception technologies of waste lead batteries Polychlorinated dibenzo-p-dioxins (PCDD) facilities, oil/water separation, precipitation, separation of Mercury from waste, treatment and recycling together with and polychlorinated dibenzofurans (PCDF) settlement, solidification and stabilisation, and UV and treatment environmental and health aspects. performance levels associated with best • Treatment processes to recover waste material for secondary use such as the available techniques for secondary lead re-concentration of acids and bases, the recovery of metals from liquid and 5.4. Guidelines on best available smelters are <0.1 ng I-TEQ/Nm3 (at operating solid photographic waste, the regeneration of organic solvents and spent ion oxygen concentrations). exchange resins, and the re-refining of waste oils techniques and provisional guidance on best environmental practices of the Best available techniques include the use of • Treatment processes to produce mainly solid and liquid fuels from hazardous plastic-free and oil-free feed material, high and non-. Stockholm Convention The Guidelines on best available furnace temperatures above 850°C, effective techniques and guidance on best gas collection, afterburners and rapid The Best Available Techniques from the crushing, shredding and sieving operations; environmental practices the is the quench, activated carbon adsorption, and BREF for the Waste Treatment Industries13 Best Available Techniques to prevent or harmonized framework and guidance dedusting fabric filters. are of special importance for meeting the control emissions; initiated by UNEP Chemicals which requirements set out in Annex III Part A of the Best Available Techniques to prevent soil provide the necessary guidance called General information on emissions from EU Batteries Directive9. Some examples on contamination; for in paragraph c) of the Article 5 of the secondary lead smelters relevant topics from this BREF are: Best Available Techniques for storage and Stockholm Convention. The use of best Air emissions from secondary lead smelting handling; available techniques and the promotion can escape as stack or fugitive emissions, Requirements for the treatment of waste Best Available Techniques on the of the application of best environmental depending on the facility age or technology. containing mercury; management of the residues generated by practices shall be promoted in some cases Main contaminants are sulphur dioxide

Requirements to be considered during the waste treatment process. and required to minimize releases of POPs (SO2), other sulphur compounds and

20 21 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

acid mists, nitrogen oxides (NOx), metals Although PCDD/PCDF are destroyed at high Collection, transport 7. Recovery (recycling) (especially lead) and their compounds, temperature (above 850°C) in the presence and storage of used lead 8. Disposal dusts and traces of PCDD and PCDF. SO2 is of oxygen, the process of de novo synthesis batteries collected and processed into sulphuric acid is still possible as the gases are cooled The scheme of life cycle of lead batteries is in acid plants. Fugitive SO2 emissions can be through the ‘reformation window’ [24]. The used lead batteries are an important shown in Figure 6. controlled by good extraction and sealing Full description of primary and secondary source of environmental hazard and it is of furnaces. NOx can be reduced using low- measures on PCDD/PCDF minimization is necessary to operate the effective system The used lead batteries system consists of NOx or oxy-fuel burners. Particulate matter given in the chapter «Thermal processes in of management of used lead batteries. The the steps 3 to 8. All these activities must is collected using high-efficiency dust the metallurgical industry not mentioned in result of the system is the environmentally be under the strict control of authorities removal methods such as fabric filters and Annex C, part II» of the «Guidelines on BATs safe handling and disposal of lead wastes as including the permit system for waste returned to the process. and Provisional Guidance on BEPs» of the well as the production of valuable secondary management activities. Stockholm Convention. raw materials. There are listed the most comprehensive Emissions of PCDD/PCDF to air during the ways of treatment and requirements smelting process The life cycle of lead batteries consists of identified by an investigation of many The most problematic PCDD/PCDF are these steps: potential sources: formed during base metals smelting 1. Production General treatment of lead accumulators through reaction of products of incomplete 2. Consumption Collected waste batteries and combustion, unburnt organic contaminants 3. Collection and sorting accumulators shall be stored in and chlorine compounds, usually by de 4. Transport weatherproof conditions in leak proof novo synthesis in the cooling zone at 5. Storage containers that are acid-resistant. temperatures between 250°C and 450°C. 6. Treatment (dismantling) Lead accumulators shall be treated PCDD/PCDF or their precursors may be present in some raw materials and there is a possibility of de novo synthesis in furnaces or abatement systems. PCDD/PCDF are easily adsorbed onto solid matter and may be collected by all environmental media as dust, scrubber solids and filter dust. The presence of oils and other organic materials on scrap or other sources of carbon (partially burnt fuels and reductants, such as coke), can produce fine carbon particles which react with inorganic chlorides or organically bound chlorine in the temperature range of 250°C to 500°C to produce PCDD/PCDF. Fig. 6: Scheme of the life cycle of lead batteries

22 23 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

separately from all other batteries and underlying skin and call for the doctor. collection under controlled conditions to separate collection of waste batteries in order to accumulators. The most important proposed measures are to 1: get the material for recovery as clean as meet collection limits given by legislation. At any rate, the treatment of lead (a) consider every material containing lead possible. The second reason for controlled There are several systems of separate accumulators shall demonstrably recover as a possible source of environmental collection is environmental protection to collection of used lead batteries. The lead and plastics of adequate purity so that and human contamination; prevent unprofessional dismantling with release simplest system is collection at sources, they can be recycled and thus, shall ensure (b) keep the work environment in of electrolyte to waters or soil. in vehicle services where the important their re-introduction in the production cycle. compliance with the national The aim of separate collection is to get the amounts of used lead batteries are arisen. The treatment shall include measures to regulations for industrial safety; used lead batteries from waste producers The services have special containers for prevent diffusive lead emissions. (c) segregate the work and eating areas i.e. to authorised treatment facilities to prevent used lead batteries. It is prohibited to open Free sulphuric acid shall be recovered. prohibit eating and smoking inside the environmental and health hazards. or dismantle waste batteries. The container working areas; The outcome of the project2 proposed the should be double-bottomed and market 6.1. General occupational health and (d) prohibit children and pregnant women extended producer responsibility where the with notice containing information on the safety recommendations for workers from working in lead recycling facilities; producers (importers) are obliged to provide waste type, hazardous properties and first- during the waste management and (e) undertake the development of (prepare, organise and finance) the system of aid instructions. The batteries should be treatment of used lead batteries educational and informative programs; , treatment and disposal. The placed into the container bottom down to The actions and certain recommended (f) ensure the use of personal protection producers will provide one or several systems of prevent spilling of the electrolyte. measures in connection with occupational equipment in working places containing health and safety should be taken to at least: improve waste management and treatment • effectively protective cloth; of used lead batteries of each treatment • hard hats and safety footwear; plant, and to achieve good environmental • daily clean-up of the used cloths; control practices. • check and clean respirators daily; From the health point of view, the proposed • protective masks which may vary preventive measures are activities that in accordance of the average lead should be observed in the occupational concentration in air; environment in order to prevent the workers (g) control the lead concentrations in the exposed to lead from suffering adverse working environment; effects of lead contamination. (h) demand periodic medical checks of lead First aid treatment that is necessary part of exposed workers; each facility in case of contact with sulphur (i) enforce showering at the end of work. acid calls for flushing the skin for 10 to 15 minutes with large amounts of water to 6.2. Collection and sorting of used lead cool the affected tissues and to prevent batteries secondary damage. Immediately remove As used batteries are a valuable source of contaminated clothing, thoroughly wash the lead it is important to provide separate Fig. 7: Container for separate collection of used lead batteries in vehicle service

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Fig. 9: Collection point operated by municipality Košice (Slovakia)

All collection systems are organised and the different battery types, a classification financed by producers (importers). It is of batteries and accumulators according to Fig. 8: Container for separate collection of used lead batteries in gas station in Slovakia expected that collection is realised on the different battery chemistry types, like the basis of agreements between operators one shown in Table 7, is recommended. The other separate collection system is the The next system is mobile collection of collection places (gas stations, services, Batteries and accumulators should be collection in gas stations. Gas station is organised by producers in cooperation municipalities) and producers (importers). sorted and prepared for separate treatment equipped with double-bottom container with municipalities. The vehicle responsible It is acceptable to realise the separate according to these battery chemistry types. where the used lead batteries are placed for shipment of hazardous wastes having collection on the basis of the agreement Due to the different characteristics of (bottom down). Take-back system in all permits and marking collects used lead between operator of collection place and batteries containing liquids and other specialised shops can be also introduced; batteries in municipalities in given term and authorised treatment facility. batteries, a differentiation between batteries the seller (distributor) of new lead batteries given place. This system enables to collect It is necessary to control that all collected containing liquids and batteries which are could be obliged to take back waste battery used batteries from households and small waste batteries will get to the authorised free of liquids is proposed (see also different when the customer is buying a new one. It is facilities as farms or small services. The treatment facility or exported in accordance recommendations for storage – chapter 6.4). required that the system is legally set in the used lead batteries can be also collected in with the Basel Convention. A mixture of liquid and non-liquid country which decides the environmentally collection points operated by municipalities Based on the different treatment containing waste batteries should be sound management of used lead batteries. in special containers. requirements and treatment options for regarded as batteries containing liquids.

26 27 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Table 7: Recommended sorting fractions of batteries and accumulators upside down, which will certainly leak (g) transport schedule and map: if possible, the electrolyte content, thus making it hazardous waste transport should always necessary to provide a shock resistant and choose routes that minimize the risk acid resistant sealed container; of possible accidents or other specific (b) containers must be well packed to the problems. This is made possible if they transport vehicle: containers should follow a certain predefined path and not be allowed to move while being restrict themselves to a known schedule1. transported. Therefore, they must be Every transport should be controlled by state bound, shrink wrapped or stacked authorities (Regional Districts) by the means properly to avoid this problem; of permits. It is recommended the permit (c) the transport vehicle should be identified should contain the following minimum with symbols: the vehicle, whether it is information: a ship a truck or a van must be correctly Name and identification of sender receiver identified, following international (address, ID number, statutory or other conventions, symbols and colours, responsible person) This classification according to battery 6.3. Transport of used lead batteries identifying the fact that corrosive Name and identification of receiver chemistries is used to give information on Used lead-acid batteries must be considered and hazardous products are being (address, ID number, statutory or other specific storage requirements (see chapter as hazardous wastes when transport is transported; responsible person, method of next waste 6.4) and on specific treatment requirements. needed. Again, the main problem associated (d) specific equipment: a minimum set of management – storage, treatment, recycling, with battery transport is the electrolyte, equipment necessary to combat any disposal) which may leak from used batteries, requiring simple spillage or leakage problems Name and identification of transporter control measures in order to minimize the risk should be provided and the transport (address, ID number, statutory or other of spillage and define the specific actions to team trained on how to use it; responsible person) be taken in event of an accident: (e) drivers and auxiliaries should be trained: Amounts of transported waste (a) used batteries must be transported inside people dealing with hazardous wastes Identification of the transported waste containers: no matter which mode of should always be trained in emergency (waste code or other identification including transport is being used, i.e. boat, train, procedures, including fire, spilling, etc. indication of hazardous characteristic) etc., used lead-acid batteries must be and how to contact emergency response The duration of the permit transported inside sealed containers due teams. Besides this, they should be aware It is strongly recommended to authorise the to the risk of leakage, which may be high of the specific kind of hazardous material is transporters (companies providing transport even if the batteries are appropriately being transported and how to deal with it; of hazardous wastes) by the Ministry of transported in upright position. The (f) personal protection equipment: PPE Environmental Affairs. transport may displace the batteries should be provided for the transport team The transport must be realised only in Fig. 10: Bad examples of used lead from their original positions, including and they should be trained in the use of vehicles that meet safety requirements. The batteries collection25 eventual box breakages or turning them the equipment, in case of any accident; vehicle must be labelled.

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explosive substances toxic substances irritant substances

Fig. 11: Labelling of hazardous cargos according to ADR

The vehicle must be furnished with first- aid set, set for elimination of accident Fig. 13: Improved packaging – steps need to be done to reach good example consequences and the driver must be Source: ABRI, 26 instructed on techniques in the case of accident.

Fig. 12: Packaging of used lead batteries ready to transport – good example Source: http://www.blacksmithinstitute.org/blog/?tag=ulab Fig. 14: Good examples of used lead batteries transport. Source: Responsible recycling of used lead acid batteries, How to manage the environmental, financial and reputational risks, Australian Battery Recycling Initiative, ABRI 26

30 31 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

6.4. Storage of used lead batteries and to the boundaries of the danger zone. electrical equipment. However, proper determines the minimum distances Storage, including temporary storage, With a sufficient degree of fire resistance earthing of the steel structure also may be from boundaries and buildings to be of waste batteries at treatment facilities the storage building can be part of another sufficient. observed. To protect the storage from shall take place in sites with impermeable establishment. If a fire breaks out in a storage facility, direct sunlight and rain, the storage area surfaces and suitable weatherproof covering The storage space can be separated into part of the stored substances may be may be covered by a roof. or in suitable containers. Table 8 shows different compartments for storing different released. The provisions for collecting of spilled recommendations on breaking down types of hazardous material each by partition The storage facility should be constructed substances and possibly released these requirements to a more detailed walls or by leaving a storage-free zone in such a way that the released substance extinguishant are the same as those specification15. empty between the compartments. Some cannot cause any harm. In particular applied in storage buildings as described These specifications are valid for storage warehouses have an inbuilt store within provisions are to be taken to prevent above. When the storage is not covered at treatment facilities including sorting the main warehouse. This interior store can polluted extinguishant from entering the with a roof, provisions for the cleaning facilities and storage facilities. be used to store particularly hazardous soil, the systems or surface water. of possibly polluted rainwater and its materials, such as highly flammable liquids controlled discharge should be in place. Storage buildings10 or gases as well as peroxides. In principle, measures and provisions The level of fire prevention and fire-fighting Storage buildings are used for storing The floors of the building are usually for storing dangerous (packaged) measures depend on many factors, such as all kinds of substances, from drums made of non-combustible material, are materials outside do not differ from the flammability of the stored substances, with flammable liquids, cylinders with liquid-tight and are resistant to the stored those for storage inside a building. The the flammability of the packaging and the pressurised gas, to packaged products such substances. amount and type of substances stored quantity of material stored. as chemicals and or chemical The roof of the building is resistant to wind- wastes awaiting disposal. They can be a blown fires, with the roof structure being standalone building or be part of another of a fire resistant construction to prevent building. fire entering the store. The degree of fire- Good design and construction of storage resistance depends on different factors buildings containing dangerous materials such as, how close the store is to the border focuses on events such as fire, explosion of the site or other buildings and the type and releases of dangerous substances, in of substances stored. particular to prevent or control them as A storage building is normally equipped much as possible. Also good management with adequate ventilation to prevent the practices and operational procedures are formation of an explosive gas mixture from important. leakages and to extract any harmful or Mostly, but not always, storage buildings unpleasant fumes. are constructed from non-combustible The use of electrical equipment can materials. The degree of fire-resistance generate sparks that might ignite a fire offered by the building itself determines in the storage building. Therefore, it is Fig. 15: Improved Storage Facility in Central America and the the minimum distance to other buildings important to use explosion-protected Caribbean 25. Outside storage (storage yards) 10

32 33 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Table 8: Proposal for the specification of the possible treatment requirement: The limit of 2,500 kilograms introduced in Table The used batteries must be placed to double- “Impermeable surfaces and suitable weatherproof covering” 15 8 as the recommended threshold for requiring a bottom containers or the storehouse must be dedicated storage building should be applied to constructed as the catch tank or the containers collection facilities like stores, car repair centres must be placed into the catch tank to prevent the etc. where batteries and accumulators are taken leakage of the electrolyte. back from final users. In these facilities batteries The storehouse as well as the containers with and accumulators are stored until a pick-up waste batteries must be marked with notice service them to treatment facilities. containing information on waste type, hazardous Used lead batteries can be stored only in special properties and first-aid instructions. The first-aid storehouses designated for storage of hazardous set must be placed in the storehouse (close to wastes. The place for storage must be covered the door easily available). and the floor must be made from acid-resistance The mobile storehouse can be used but the materials. It is forbidden to store used lead temperature of the ambient air must be batteries near heating sources or fire because the measured because the temperature over 40°C danger of explosion is present. It is also forbidden can cause the danger of spontaneous explosion. to smoke or use open fire in the storehouse. It is recommended to regulate the requirements The storehouse must be equipped with air for storage of hazardous waste by legislation exhaustion system. The storehouse must be and to submit special permits for storage of connected to sewage system or retention tank. hazardous waste by authorities (Regional

Fig. 16: Mobile storehouse of hazardous wastes

34 35 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Districts). accumulators must be limited to the storage of The intention is that this small scale storage for this type of batteries; portable batteries and accumulators does not it shall also be limited by a maximum to need a permit for the storage of hazardous storage quantity and/or a maximum storage wastes, as long as the batteries are not stored time of the average turnover of batteries. longer than one year (interim storage). Proposed limits are: The interim / small scale storage for portable - a maximum storage quantity of 7,5 t batteries and accumulators has to fulfil technical (amount for a full ‘medium-size’ truck), requirements such as: - a maximum storage time of 1 year; suitable containers are to be used (see Table 9), this interim / small scale storage facility all storage areas have impermeable surfaces should fall under the same inspection (see Table 8), requirements as the regular storage facilities the storage building and/or the outdoor which need permits. storage area are covered with a roof (see Table 8), Table 9 shows recommendations on which the storage building or area is inaccessible for requirements should be fulfilled in order to unauthorised person. make a container suitable for waste battery In addition storage15. an interim storage for portable batteries and

Table 9: Proposal for the specification of the minimum treatment requirement: “suitable containers” 15

36 37 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Treatment of used lead Treatment requirements with regard to the In specific cases the removal of fluids is not batteries battery chemistry. feasible, e.g. if the electrolyte is solidified (lead acid gel accumulators). In such cases The treatment of used lead batteries is Requirements for removal of fluids the recycling process must be optimised sometimes called wet technology, as the According to the EU Batteries Directive individually with the aim to minimise liquid electrolyte is present. (2006/66/EC) Article 12(2) and Annex III, Part emissions and hazards to human health as A9, waste battery treatment shall, as a minimum, well as to achieve high recycling efficiency. include removal of all fluids and acids. During the treatment processes the Table 10 specifies specifications for removal environmental hazard must be taken into of fluids and acids as recommended in [15] account. The collecting vessel must be acid- in order to limit the environmental impact of resistant, usually having special pavestone these processes. bottom and walls covered by resistant

Table 10: Proposal for the specification of the minimum treatment requirement: “Removal of all fluids and acids, their collection and treatment” 15

Fig. 17: Typical used lead batteries recovery process 7

The Technical Guidelines1 describes The battery scrap obtained from the breaking following treatment steps and two methods process is a mixture of several substances: in order to isolate the metallic lead from this metallic lead, lead oxide (PbO), lead sulphate mixture that may be applied: (PbSO4) and other metals such as calcium (Ca), battery breaking – including a description copper (Cu), antimony (Sb), arsenic (As), tin of processes and potential sources of (Sn) and sometimes silver (Ag)1. environmental contamination, As which potentially are emitted lead reduction including a description of from the treatment processes e.g. electrolyte, pyrometallurgical (also known as fusion- dust, sulphur dioxide (SO2) are described and reduction method) and hydrometallurgical some measures for are methods (also known as electrolytic mentioned. method) and potential sources of Relevant requirements for lead-acid environmental contamination, accumulators derived from the Technical lead refining - especially describing Guidelines1 are included in Chapter 10.2 - pyrometallurgical refining and potential Special care on batteries and accumulators sources of environmental contamination. with liquid electrolyte and Chapter 6.2 -

38 39 foil and stainless steel. The space around Recovery of used lead collecting vessel is monitored for leakage. batteries The main environmental issues of the lead industry are air and The recovery of secondary lead consists of and the generation of hazardous wastes. smelting, refining and doping. The facilities generally have their own wastewater treatment facilities and wastewater recycling is usually practised. Many wastes are reused but the major item is leach residue that has a high environmental impact. Some local aspects, like noise, are relevant to the industry. Due to the hazardous nature of some solid and liquid waste streams, there is also a Fig. 18: Typical used lead batteries recovery process10 significant risk for . As it is not purpose of the guidelines to describe into the detail some technical specifications but the waste management it is recommended to follow guidelines14, 24.

Fig. 19: Secondary lead installation of the company Mach Trade (Slovakia)

40 41 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

recommended, however, for more details to CX and related processes). follow chapter 5.2 Best Available Techniques Lead sulphate can be separated and sent Reference Documents of the European to an installation capable of treating the Commission where BREFs contain many sulphur content in the gases for example specifications which are relevant for waste one of the direct smelting primary lead battery treatment. Nevertheless, several processes. alternatives are used to deal with the sulphur The sulphur may be fixed in the slag or as a contained in the battery materials from the Fe/Pb matte. environmental point of view. Paste de-sulphurisation prior to smelting can Prior to smelting, the lead sulphate paste reduce the quantity of slag produced and, may be de-sulphurised by reaction with depending on the smelting method used, the Fig. 20: Costa Rica – Pb Metals SA25. sodium carbonate or sodium hydroxide (in the amount of sulphur dioxide released to the air.

Recovery of lead from products of wet (Engitec) processes use hammer type technology is operated in metallurgy part of mills to crush the whole batteries. The the technology. crushed material then passes through a There are two main types of process for the series of screens, wet classifiers and filters recovery of lead from automotive batteries: to obtain separate fractions containing a. Batteries are drained of acid and fed metallic components, lead oxide sulphate whole into a blast or shaft furnace (Varta paste, polypropylene, non-recyclable process). Whole batteries and fluxes are plastics and rubber and dilute sulphuric fed into a blast furnace via a seal and acid. Some processes use a second oxygen enriched air is used in the blast. milling stage before the plastic fraction is Antimonial lead bullion is produced, along finally treated. Polypropylene is recycled with silica based slag and a lead/iron as far as possible. The sulphuric acid matte that can be recovered in a primary drained from the batteries is neutralised lead smelter. Organic components in the unless there is a local use for it and the furnace off-gases are oxidised in an after- sodium sulphate produced can be re- burner and the gases are then cooled and crystallised and sold. These are strongly filtered in a fabric filter. The filter dust is de- market dependent options. chlorinated and returned to the furnace. b. Batteries are drained of acid broken and As it is not purpose of the guidelines to separated into various fractions using describe into the detail technical specifications automated proprietary equipment (MA of the lead recovery metallurgical and CX processes). Both the MA and CX processes but the waste management it is Fig. 21: Example of scheme of the wet treatment technology (Engitec)16

42 43 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

The lead and lead paste are transported to the smelting reactor that can be: rotary furnace, reverberatory furnace and blast or electric furnace, rotary kiln, ISA Smelt furnace, electric furnace.

Fig. 22: Example of lead rotary furnace 27 Fig. 23: Example of reverberatory Fig. 24: Examples of blast furnace 29 furnace 28

44 45 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

paste and reductant are continuously fed which are tapped periodically. The waste into the furnace and lead bullion is tapped gas contains CO and is burnt and flue dust is periodically. When the process vessel contains collected. the maximum volume of slag, reductant and The furnace is fed with input materials fluxes are added to produce high antimony that are lead metal and lead pasta, resp. bullion and a discard slag. The slag may also dust outlet, slag formers, reductant and be reduced in a separate furnace. calcinated soda. After feeding the input The electric resistance furnace is used for opening is closed and the furnace is heated. complex secondary materials and uses After the smelting the content of furnace is Fig. 25: Example of rotary kiln 30. an open slag bath covered by coke. Raw poured out to pre-heated mould. The slag materials are fed onto the top of the bath remains in the top part of the mould and the where they react to produce metal and slag, lead is pin down to ingot mould 10, 11, 16.

Fig. 26: Example of ISA Smelt furnace 31. Fig. 27: Furnace of Industrias Meteoro S.A. - Dominican Republic 25.

Rotary and reverberatory furnaces can be produce a slag that is stable. The bulk of the either gas or oil fired. Oxygen enrichment sulphur in the charge is fixed in the slag, is used in several installations. Smelting which is a sodium-iron-sulphur compound is usually carried out in batches, slag and with small amounts of lead and other metal are tapped out separately and batches metals. of slag are treated to recover more lead and In the ISA Smelt process de-sulphurised

46 47 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

The following tables give input and output After the recovery of lead from battery scrap copper, silver, bismuth, antimony, arsenic and electrically and selectively reduce all lead balances for some lead plants in Europe as the refining of crude lead is operated. Lead tin. Lead recovered from secondary sources compounds to metallic lead, such as in the an example 11. bullion may contain varying amounts of may contain similar impurities, but generally PLACID technology. antimony and calcium dominate. The chemical concept behind the Table 11: Example of input and output data for a battery There are two methods of refining crude lead: electrolytic process is the conversion of recovery plant without de-sulphurisation a) electrolytic (hydrometallurgical method) all lead compounds into a single chemical refining, which refining uses anodes of species, lead in oxidation state +II (Pb2+ or de-copperised lead bullion and starter plumbous lead) in this case, which is then cathodes of pure lead, electrolytically reduced to produce metallic b) pyrometallurgical (also known as fusion- lead. The electrolysis deposits lead as reduction method) refining that consists dendrites or sponge, which are subsequently of a series of kettles, which are indirectly shaken off and collected on a conveyor heated by oil or gas. belt and pressed to form platelets of pure lead (99.99%), which can then be conveyed Hydrometallurgical Methods to a melting kettle for casting into ingots. The objective of the hydrometallurgical The whole extraction process can be run methods, or electrolytic methods, is to continuously 24 h/d, without interruption.

Table 12: Example of input and output data for a battery recovery plant with de-sulphurisation

Fig. 28: Diagram of an electrolytic lead process1.

48 49 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Although it may be sometimes costly when appropriate separation of raw materials, it is a Pyrometallurgical Methods purity grades (up to food grade quality). considered as an isolated plant, this process technological solution to overcome the lead The objective of the pyrometallurgical The metallic fraction and the lead provides good results when linked to a low refining processes1 . methods (fusion-reduction) is to chemically compounds derived from the de- temperature smelting plant since, with the reduce all metallic compounds to their sulphurization and neutralization processes metallic or reduced forms by means of are then added to the furnace and smelted heating and providing adequate fluxing and with fluxing and reducing agents. The reducing substances. necessary heat is provided by several sources depending on the specific method Prior to smelting, some methods may oil, gas, coke, electricity, etc. be employed to de-sulphurise the lead The fluxing agents, which melt at a sulphate paste by reacting it with a mixture temperature below the lead compounds

of sodium carbonate (Na2CO3) and sodium melting temperature, are added not only hydroxide (NaOH), such as in the CX and to reduce the lead smelting temperature, related processes, converting the lead but also to provide a liquid solvent, which

sulphate (PbSO4) to lead oxide (PbO). traps several unwanted compounds during Sometimes the de-sulphurizing agent may the smelting and reducing processes. As 1 Fig. 29: Electrochemical process in hydrometallurgical lead production . also be iron oxide (Fe2O3) and limestone the flux starts to be contaminated with

(CaCO3). This procedure reduces the amount all sort of impurities from the smelting of slag formation and also, depending on process the formation of slag also starts. The the smelting method, the amount of sulphur physical and chemical properties of this slag,

dioxide (SO2) released into the air. However, which are important characteristics to be other methods simply add controlled considered in a later treatment, are entirely amounts of lead sulphate as well as de- dependent on the chemical composition of sulphurizing agent directly into the furnace. the flux that is used. The acid electrolyte must also be treated Reducing agents, on the other hand, are before its lead content may be sent to the added with the purpose of reducing the

smelting furnace. This is carried out by lead oxide (PbO) and hydroxide [Pb(OH)2] neutralization of the electrolyte solution to metallic lead. It is usually a carbon based with sodium hydroxide, which precipitates compound such as coke, coal fines or other

the present lead as lead hydroxide [Pb(OH)2]. natural carbon source. This compound is then removed by After the process had been properly decantation or filtration and directed to the balanced, the melted metallic lead starts furnace. The remaining solution, sodium to accumulate in the bottom of the

sulphate diluted in water (Na2SO4), may be vessel. However, as mentioned earlier, it is Fig. 30: Diagram of a lead smelting pyrometallurgical process1. further purified and the salt isolated in high sometimes heavily contaminated with other

50 51 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

metals of economic value. Therefore, this lead bullion must undergo a refining process before pure lead can be recovered from it1.

Fig. 32: Lead bars as the final product

The process of lead scrap recovery produces emissions to air and waste waters. The main emissions to air are [7]: sulphur dioxide SO2, other sulphur compounds and acid mists; oxides of nitrogen NOX and other nitrogen compounds; metals and their compounds; dust; VOC´s and PCDD/F [11, 14]:. Fig. 31: Diagram of more detailed lead refining process11.

52 53 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Table 13: Example of mass release of metals from battery scrap recovery the process and the practices used by the in some plants in Europe 7 operators. The of process water and rainwater is common. Cooling water from the granulation of slag or the cooling pond is usually recirculated in a closed circuit system. Typical components in waste water from some processes are given in Table 157.

Table 15: Example of typical waste water analysis 7

Table 14: Example of national emission limits for standard conditions (dry gas) for secondary lead technology (Slovak Republic)

The battery breaking and washing stages surface water and consequently this water produce an effluent which is acidic is also treated and reused. It is common and contains lead and other metals in practice to discharge a bleed of this sealed suspension and solution. This effluent is water circuit after further treatment and neutralised and the water is recycled in analysis. Road and surface contamination the process. If possible, the acid is used is minimised by the frequent wet cleaning elsewhere. A portion is usually bled from the of roads, hard standing areas, lorry and by system to control dissolved salts. Cooling cleaning up spillages. water can also arise from cooling the The quality and quantity of waste water crushing process7. depends on the process used, the These processes also produce contaminated composition of the raw materials used in

54 55 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Disposal of used lead carbonate (Na2CO3) or calcium carbonate and their impacts, batteries It is recommended to ban the disposal of (CaCO3), thus producing sodium sulfate f) conclusions from the environmental

used lead batteries or fractions of their (Na2SO4) or gypsum (CaSO4) which, after impact assessment study. The main objective of the environmental dismantling. When no viable end market removing lead sludges by filtration, can policy in the field of used lead batteries is is available it should be permitted only in be further purified and sold to the cement The site shall have: to maximise the separate collection, reuse landfills or underground long-term storages industry or the building trade. a) an information board, lead as valuable recoverable resource and to that are designed and operated for disposal Thus, despite some cost increases in b) an approach road to the landfill and minimise disposal of used batteries as mixed of hazardous wastes. Such landfills of recycling, calcium slags have found some paved carriageways at the landfill site, municipal waste. underground storages must be authorised use as a raw material in cement production c) a fence and lockable gates, by national competent authorities. which has been employed in road building, d) a weighing-machine, According to Article 14 of the EU Batteries bricks, etc., with promising results1. e) operating premises containing all the Directive (2006/66/EC) [9] the European It is recommended to ban the of In such cases of production of hazardous necessary equipment, Member States shall prohibit the disposal in used lead batteries. waste the location of the landfill for f) fire extinguisher, landfills or by incineration of waste industrial hazardous wastes must be taken into g) a sealing system, and automotive batteries and accumulators. 9.1. Landfills for hazardous wastes account: h) a drainage system with a leachate However, residues of any batteries and Some wastes - unrecoverable wastes a) secure distance from the boundary of collection tank, accumulators that have undergone both produced during the lead recycling process the future landfill site to residential and i) a drainage system for landfill gas and an treatment and recycling may be disposed of will not be recycled any further or reused recreation areas, waterways, water bodies installation for its use or disposal, except in landfills or by incineration. and, therefore, will need a sound destination and water sources, for landfills for wastes where landfill gas for disposal. It must be stressed that usually b) geological, hydrological, hydrogeological is not likely to originate, From the above, it becomes clear that such wastes have lead contents as high as and mechanical-geological conditions in j) a groundwater monitoring system, waste management such as landfilling 2-5% and must be treated as hazardous the vicinity, k) a landfill gas monitoring system, except and incineration cannot be considered as wastes, even if the lead is not leachable, and c) the protection of nature, landscape and for landfills for wastes where landfill gas an environmentally sound management thus requires a destination in a regulated cultural heritage in the vicinity, is not likely to originate, of used lead batteries, not only for hazardous waste landfill site. d) the acceptable burden on the territory, l) a drainage system for surface water, economic reasons but also for health and Stabilized slag from refining steps is the e) possible extreme meteorological effects m) an installation for cleaning vehicles, environmental reasons. major hazardous waste formation from the whole process and the sodium slag arising However, there are cases in which the from the utilization of sodium carbonate disposal is necessary, especially when no does not have any use due to its physical treatment and recycling facilities exist or and chemical properties, and, therefore, it is the fractions got from dismantling of used being directed to hazardous waste landfills. batteries are not suitable for consequent There are other pollution sources produced recovery in the country which is not the during the treatment such as effluents and European Member States. electrolytes that may be treated by sodium Fig. 33: Landfill foundation

56 57 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

n) other installations necessary for landfill in such a way as not to damage the and use of landfill gas shall be carried on in water (pH, TOC, phenols, , operation of the landfill. sealing and drainage systems of the landfill; a manner which minimises or does not have fluorides, hydrocarbons, etc.), the first layer of deposited waste may only any negative effects on the environment d) topography of the landfill. Any landfill must have a fence in order to be compacted if it is 2 m thick; the first and human health. prevent free access to the landfill. The gates layer may not contain waste which could For monitoring groundwater quality in the must be locked outside operating hours. damage the base of the landfill. There shall The operator of the landfill must provide the vicinity of a landfill site, a sufficient number The system of control and access to the be a suitable peripheral drainage system monitoring of: of measuring points must be constructed; landfill must contain measures to prevent of suitable dimensions for the drainage of a) meteorological data (precipitation, there must be at least three, one in the dumping of wastes at the landfill without a surface water from the vicinity of the landfill. temperature, wind, evaporation, groundwater inflow region and two in consent of the landfill operator. On landfills Appropriate measures shall be taken at humidity), the outflow region. The original values of where an artificial sealing barrier is used, any landfill in order to control leachate and b) emission data (amount and composition groundwater quality must be ascertained the geological substratum of the landfill, manage the leachate regime providing of leakage, emissions of gases), before commencement of landfill considering the morphology of the landfill, in particular for control of water from c) measurement of quality of underground operations. must be sufficiently stable to prevent precipitations entering into the landfill settlement that may cause damage to the body, prevention of surface water and artificial bottom sailing. groundwater from entering into the landfill During the operation of a landfill measures waste, drainage and collection of leachate, shall be taken to minimise effects of the the treatment of leachate collected from the landfill on the environment caused by landfill in order to comply with discharge emissions of odours and dust, wind-blown values into the sewerage system or recipient material, noise and traffic, birds, vermin and or transport of the leachate to a suitable insects, formation of or fires. sewage treatment plant. The landfill must be equipped and operated The emplacement of waste on the landfill in such a way that dirt from it, caused site shall take place in such a way as to mainly by the vehicles/means of transport, ensure stability of the waste deposited and is not dispersed onto public roads and the associated structures of the landfill and surrounding land. the necessary construction equipment, At the landfill site waste shall be deposited particularly in respect of avoidance of in layers 0.3 to 0.5 m thick, which are slippages. then compacted; the working layer after Landfill gas shall be collected from all compacting shall be no more than 2.0 m landfills receiving . The thick. Waste shall be compacted no later collected landfill gas must be treated and than the day following its dumping unless used to produce energy; if the landfill gas provided otherwise. The first layer of waste collected cannot be used to produce energy, shall be deposited at the bottom of the it must be flared. The collection, treatment Fig. 34: Artificial geological barrier for landfill

58 59 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

consignment is recorded for future adverse consequence” on the environment. reference. Once each disposal zone has been filled, walls (known as stoppings) are erected 9.3. Accepting waste for disposal between the rock salt pillars to create Waste may only be accepted at a landfill physical barriers between storage zones. The or a long-term storage if the waste holder operation of long-term storage must be held presents to the operator of the landfill or in that way that no harm for underground a long-term storage with each delivery of water or ambient air is ensured. waste document on quantity and type of Usually underground mines undertake waste delivered, a consignment note and extensive research, establish detailed design identification notes for hazardous wastes, and operational procedures and produce details about the characteristics and thorough qualitative and quantitative composition of waste in the form of report short and long-term risk assessments, all on analytical control of wastes. supported by complementary evidence. Thanks to the geological and hydro- At the time of delivery of the verification of geological features that so effectively isolate whether the required waste documentation the underground beds of rock salt from the is complete and correct, verification of the Fig. 35: Artificial barrier using HDPE foil for landfill biosphere, even in the worst case scenario data, and other conditions agreed for waste the facility is likely to have “little or no acceptance, control of quantity of waste 9.2. The underground long-term storage for hazardous wastes Hazardous wastes including used lead batteries can be stored in long-term underground storages as closed salt- or potash-mines in appropriate containers. The very strict controls on the accepted types of waste are undertaken at the mine in drums or bulk containers. After verification the used lead batteries, if accepted by the mine, are loaded into transit capsules for transport underground. Drums are then offloaded and stacked in their allocated safe storage areas to a maximum height determined by their Fig. 36: Foundation of landfill contents. The location of each waste Fig. 37: Balancing of container at the acceptation of the waste for disposal

60 61 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

delivered, visual inspection of waste delivery Transboundary that all marketed battery systems contain following (technical) information: in order to verify declared information movement of used lead at least one Annex I constituent, namely Chemical composition of the wastes concerning origin, characteristics and batteries the electrolyte (which is either an acid Y34, (data from literature, no chemical analysis composition of waste, ensuring controlled alkali Y35, or a solvent Y42). Regardless of required in the case of batteries). random sampling of waste and tests and The transboundary movement of used this classification, waste batteries are to be A technical description of the waste analyses of waste in order to verify given lead batteries is subject of the Basel classified as hazardous waste in accordance treatment / recycling process including a information about origin, characteristics Convention on the Control of Transboundary with Article 1,1,b of the Convention anyhow. mass flow scheme. and composition of waste and recording Movements of Hazardous Wastes and Their Therefore every transboundary transport of Information of the recovery (R-operation) accepted waste must be done. The operator Disposal. The import and export are a matter waste batteries is to be notified. or disposal (D-operation) of the output of of the landfill or a long-term storage shall of notification of state authorities of both If the country of import is the EU Member the treatment / recovery process. confirm the acceptance of the waste to the exporting and importing parties according State it is necessary to follow requirements Relevant information on the license (date waste holder, indicating the date and time to the article 6 of the Convention. of Regulation on shipment of waste of expire, licensed wastes). of its acceptance. Such notification shall contain the [18]. The used lead batteries are defined Information on emissions (reference to declarations and information specified in as”A1160 Waste lead-acid batteries, whole BAT, mandatory or plant specific emission Annex V A, written in a language acceptable or crushed” and only import for recovery limits, current measurements of the to the State of import. Every shipment must is allowed, the import for disposal is emission to air and/or water, type of applied be accompanied by the documentation allowed only the Community and its emission abatement technique). containing information defined in Annex V B Member States, have concluded bilateral or Existence of a quality assurance system or of the Convention. multilateral agreements or arrangements an environmental performance assessment. The used lead batteries are classified as with the country of export or in cases on The Competent Authority shall scrutinize “A1160 Waste lead-acid batteries, whole exceptional grounds during situation of these documents and consent in the or crushed” with Y-code “Y31 Lead; lead crisis, peacemaking, peacekeeping or war transboundary movement only if the compounds” and H-codes “H1 Explosives”, according to the Article 41 of the Regulation. environmentally sound treatment appears “H8 Corrosives” and “H11 Toxic”. The procedural requirements are described to be secured. Entry A1160 refers to “waste lead-acid in Article 44 of the Regulation with the If the waste lead batteries are shipped batteries, whole or crushed”, while entry requirement of prior written notification in into countries that signed international A1170 refers to “unsorted waste batteries accordance with Article 4 of the Regulation convention ADR [19] or RID [20] the excluding mixtures of only list B batteries and the conditions for shipment of the requirements of the convention must be and waste batteries not specified on list B waste are given by Article 44 (4) of the met. containing Annex I constituents to an extent Regulation. For the transport of batteries and to render them hazardous”. To allow the Competent Authority a full accumulators the European Agreement The mirror entry B1090 refers to “waste evaluation of the foreign waste treatment concerning the International Carriage of batteries conforming to a specification, or recycling process the notifier of the Dangerous Goods by Road (ADR) [19] has excluding those made with lead, cadmium transboundary transport should at least to be considered. This is an agreement or mercury”. However, it can be assumed provide the Competent Authority with the that prescribes requirements for the

62 63 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

transboundary transport of dangerous acid, electric storage, Class 8. Black plastic wrap is not acceptable. (Slip sheets must be used between the goods by road vehicles. The ADR specifies A minimum set of specific equipment to layers to minimise the potential for short detailed requirements for the transport of combat spillage or leakage during transport circuit and post penetration. Heavy duty the different battery types e.g. batteries, must be available in the transport vehicle. cardboard slip sheets are preferable to wet, filled with acids. Drivers and auxiliaries should be trained. Masonite or chipboard because they are Effective personal protection equipment recyclable, and small spills can be absorbed 10.1. General requirements for is to be provided and available in the and are visible. Polystyrene slip sheets “transport” / ADR transport vehicle. are not to be used as they are difficult Requirements regarding the transport Transport schedule and route is to be and costly to recycle (suppliers may incur of lead-acid batteries from the Technical selected in a way that reduces the risk of an environmental disposal levy to cover Guideline for the Environmentally Sound possible accidents. the costs of disposing of any polystyrene Management of Waste lead-acid Batteries [1] In principle the provisions of the ADR received).) 26. were summarised [4] as follows: are applicable to the transport of waste Used batteries must be transported inside batteries. However, according to Vol. shock resistant and acid resistant sealed II, clause 598 of the ADR ‘used storage containers. batteries’ are not subject to requirements of In order to prevent move of containers ADR when: during transport they must be well packed their cases are undamaged; to the transport vehicle (i.e. they must be they are secured in such a way that they bound, shrink wrapped or stacked properly). cannot leak, slip, fall or be damaged, e.g. by The transport vehicle should be identified stacking at pallets; with symbols (transport of corrosive and there are no dangerous traces of alkalis or Fig. 39: Examples of bad packaging hazardous products). acids on the outside of the articles; before transport, ABRI 26. The container shall be labelled with UN- they are protected against short Number 2794 BATTERIES, wet, filled with circuiting. (Black plastic impedes inspection by the transport driver and facility staff, who will make a judgment on compliance with environmental and dangerous goods regulations, and this standard, based on observation. For example, any liquid on or leaking from the consignment could be deemed as leaking battery acid (electrolyte). Clear plastic wrap is the best option.) 26. Fig. 40: Examples of bad packaging Fig. 38: Examples of good packaging before transport, ABRI 26. Polystyrene slip sheets are not acceptable before transport, ABRI 26.

64 65 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

(There must be at least two vertical straps tying the 10.2. Special care for batteries and Potential Sources load to the pallet) accumulators with a liquid electrolyte of Environmental (Batteries need to be wrapped as well as strapped) Batteries and accumulators with free liquid Contamination electrolyte may cause specific damage during storage and transport. They shall 11.1. Battery Breaking Process be kept separately based on the nature of Each step of handling with used lead batteries their electrolyte (acidic, alkaline or organic) is possible sources of contamination that may and stored in tight, leak proof and stable occur in the recovery processes. It is described containers. It is recommended to use UN- shortly and should be understood as the tested and correctly labelled containers predictable list of common contamination even for intermediate storage to avoid sources and where to look when searching extensive manipulation/repackaging when for them. Specific sources of contamination Fig. 41: Examples of bad packaging before transport, ABRI 26. the batteries are shipped. will have to be determined in the light of the Lead acid batteries are listed under UN- process employed. (Broken pallets are unacceptable) Number 2794/Class 8, alkaline batteries The common sources of environmental (The pallet load needs horizontal as well as under UN-Number 2795/Class 8. impacts in the battery breaking process are vertical strapping) Accumulators with an organic electrolyte then: until recently have not been in common use (a) spilling batteries - acid electrolyte and and therefore are not mentioned in the ADR. lead dust contamination source: battery Sealed batteries/accumulators (e.g. spillage may be a very common source of consumer batteries type AA, AAA, C, D) are environmental contamination as well as normally not regarded as batteries with human health injuries since the electrolyte liquid electrolyte. However, sealed lead acid is not only a strongly corrosive solution but batteries should be regarded as accumulator also a good carrier of soluble lead and lead with liquid electrolyte since the acid may particulates. Therefore, if this solution spills leak out quite easily due to mechanical in an unprotected area, it may contaminate damage. It is therefore recommended to the soil or injure workers. Besides, after collect, store and transport seal lead acid spilling on unprotected soil, the soil itself batteries in the same way as normal lead becomes a source of lead dust once the acid batteries. solution evaporates and the lead becomes incorporated into soil particles which may blow by wind or raised by vehicle transit; (b) manual battery breaking – source of human health injury and environmental Fig. 42: Bad and unacceptable examples of transport conditions damage through heavy spillage and lead

66 67 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

contaminated dust formation: manual 11.2. Lead Reduction Process used, they are usually recycled in the same tar formation, since its reduction process breaking usually relies on primitive The common sources of environmental smelting process since they may contain consumes all organic materials. On the other tools, poorly protected workers and no impacts in the pyrometallurgical lead as much as 65% of lead. However, the care hand, the less controlled the reduction environmental protection whatsoever. The reduction process are: and maintenance of these filters may be an process is, the greater are the tar emissions, situation is even worst in the case of sealed (a) lead compounds derived from the breaking important source of contaminating dust, especially in artisan foundries. If the batteries, which are not easily drained, process – lead and lead compounds in dust which could pose a risk to the human health reduction furnace has filters, the emission increasing dramatically the risk of heavy and water: the separated and fine materials and the environment. Besides, over-used of tars is an even greater problem since they spillage and damage to human health. from the breaking process are usually wet, filters no longer capture lead dusts as are very pyrogenic and may produce fires in Therefore, it should be avoided at all costs; since the main processes of separation are originally intended and the dust emissions the filtration plant, thus increasing the risk (c) mechanical battery breaking – source of based on water techniques. However, if they from the fusion oven becomes an important of an accident and the possibility of a rogue lead particulate: the process of breaking are not incorporated in a fully automated source of contamination. Finally, one must emission. The introduction of afterburners batteries through crushing on hammer process, they will have to be transported also realize that the furnace inlet is itself to complete the combustion of gases from mills may spread lead particulate. However, from the breaking facility to the reduction a source of lead dust to the environment, the furnace is the usual solution to this the fact that the mill is sealed and uses facility and some muddy and/or watery since it can be an open system. The high problem, but a complete restructuring copious quantities of water the formation material may spill and fall from the transport temperature fume that leaves the furnace of the process, removal of organics for of such particulates is prevented; system. After drying, these materials become inlet and tapping area, for example, have example, may present better perspectives;

(d) hydraulic separations – contaminated a powder and may contaminate the factory a high lead content, and will be readily (f) chlorine (Cl2) and chlorine compounds water leakage: the hydraulic separations, and its surroundings as fine lead dusts; absorbed by the human body; emission: an initial separation of the

both metallic from organic and heavy (b) drosses – lead contaminated materials: (d) sulphur dioxide (SO2) emissions – the materials allowed to enter the reduction organics from light organics, are usually drosses are formed while the fusion process percentage of sulphur from a given process reduces the chlorine emission

preformed inside sealed machines and takes place. Its function is to remove amount of lead scrap load that leaves the considerably. Cl2 is source for PCDD/

with a closed water system. However, if materials that are not easily incorporated reduction system as sulphur dioxide (SO2) is PCDF formation during lead smelting any water leakage occurs, it will be heavily or wanted in the crude lead. However, highly dependent not only on the furnace thermal process (see chapter 5.4). contaminated by lead compounds; these drosses still contain lead that can be conditions, but also in the kind of skim However, increasing amounts of PVC in the (e) plastic and ebonite chips – contaminated recovered and are recycled in the fusion material being formed. As a general trend, furnace increases the chances of chlorine wastes: ebonite removed from the process. In order to accomplish these this number may fall between 0% and 10% emissions. The major part of it is absorbed breaking process may pose a problem, task, the drosses must be removed and and it is significantly reduced if the flux by the basic skims of calcium or sodium, since they are usually contaminated transported to the furnace charging bay, but used is a mixture of iron and sodium based however some of the chlorine is chemically by levels as high as 5% (w/w) of lead. since they are usually a dusty material and compounds producing sodium skims and converted into lead chloride which is Therefore, it is important that the final occasionally powdery (copper dross), they pyrites. Ebonite also has 6-10% of sulphur volatile under furnace conditions but

traces of lead are removed by a second may be a source of lead contamination while that may contribute to the SO2 emission if captured by dust filters as the temperature wash, preferably in an alkaline solution, being transported; it is added to the furnace charge; decreases; followed by another rinse prior to further (c) filters – lead contaminated dusts: furnaces (e) organic material combustion – tar (g) slag production: this is the majority of the treatment or disposal 1. need filters in order to capture lead dusts formation: a well structured and controlled waste production during the reduction formed in the fusion process. After being refinery does not need to worry about process. As an average picture, around

68 69 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

300-350kg of slag is produced for each eliminates this problem; ton of metallic lead, depending on specific (c) skim production and removal – metal Economic aspects of factors of the process and the kind of contaminations: the skim production and environmentally sound residue being formed (calcium or sodium removal from the refining kettle while skims), and around 5% (w/w) of this slag is refining unwanted metals from the crude composed of lead compounds. Therefore, lead may pose threats to the human health special consideration must be given to and environment due to the physical the leachate that may be produced if an characteristics of the skims. Sometimes they unstable water soluble slag comes into are in the form of a very fine and dry dust contact with water or moist air. A purpose with a high percentage of lead and other built under cover storage bay to store this metals, it is important to provide adequate material must be planned well in advance covered or sealed transport, storage and in order to avoid human health and a sound destination to this potentially environmental problems 1. hazardous by-product;

(d) chlorine (Cl2) tin (Sn) removal and recovery – Fig. 45: Examples of bad used lead 11.3. Lead Refining Process chlorine gas release: If the tin is removed by batteries management The refining process can be a polluting chlorine gas for later recovery, then this is a very Fig. 43: Examples of bad used lead Source: http://www.blacksmithinstitute.org/ process if some control measures are not delicate procedure. The intake of gas is planned batteries management blog/?tag=ulab taken. Some sources of environmental in order avoid chlorine release, i.e. the gas reacts Source: http://www.worstpolluted.org/projects_ impacts in the lead refining process are: with the tin before reaching the surface of reports/display/78 (a) over heated lead – lead fumes: sometimes molten lead. However, an uncontrolled addition the lead from the reduction process is of chlorine may release the poisonous gas to introduced directly into the refining kettle, the environment. Besides, the storage and which may be as hot as 1,000ºC. Therefore, handling of chlorine is itself a delicate operation it is not uncommon that the lead refining due to its corrosiveness and toxicity;

process produces large amounts of lead (e) oxygen (O2) enriched air tin (Sn) removal vapour. Ideally lead should be tapped from – lead fume: while the air is being passed the furnace directly into a lead bath or inside the molten metal, the nitrogen

allowed to cool prior to pouring; (N2) present in the air does not react. The Fig. 46: Examples of bad used lead

(b) sulphur dioxide (SO2) emissions: the copper consequence of this is that the gas bubbles batteries management removal by addition of elementary sulphur violently in the surface of the metals Source: ABRI, 26 may produce large quantities of sulphur releasing dusts and metallic fume1. Fig. 44: Examples of bad used lead

dioxide (SO2), since sulphur oxidizes batteries management readily in the presence of oxygen at the 11.4. Bad examples of potential Source: http://www.blacksmithinstitute.org/ oven temperatures. The use of iron pyrites contamination of the environment blog/?tag=ulab

70 71 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

management of used lead lead batteries in the country or abroad. If the different from the prices in other regions. that the lead environmentally sound batteries price of the treatment of used batteries is The simplified scheme of waste, finance and management process is deeply embedded minus the producer / importer must pay also information streams in used lead batteries in social and economic aspects that The project2 proposes the application of the costs connected with treatment. EPR system is given in Figure 47. dictate several problems as well as several extended producer responsibility as a If the producer / importer fulfil his obligation solutions not covered and which could system for financing the environmentally individually he has to finance the separate Last but not least, it must be understood not possibly be covered in this guideline. sound management of used lead batteries collection of the amount of used batteries according to the model of EU stated in the that is equivalent to his collection share. If Battery Directive9 The extended producer the producer / importer join the collective responsibility is based on the responsibility scheme then he pays to the system money of producers / importers of batteries to equal to the amount of batteries that he put establish and operate system of separate on the market and rate. The rate reflects real collection, treatment and recovery of costs of separate collection, treatment and used batteries what means also to finance recovery of used batteries, as well as the whole system. The producers can fulfil costs of the information campaigns and the their obligations individually or collectively operation of the collective scheme itself. through collective scheme. However, obtaining secondary lead Producers must cooperate with producers from used lead batteries is economically (holders) of used batteries, as services attractive, cutting about 25 % from the and maintenance facilities as well as with energy bill compared with primary municipalities to provide for separate lead. In addition, batteries are a ubiquitous collection of used batteries in order to fulfil product with a predictable lifetime, and legal limits of collection, given usually as a the large market for recycled lead creates percentage of amount put on the market. economies of scale. As a result, battery The industrial association or governmental manufacturers rely heavily on secondary authority (ministry, agency…) collects lead, most of it sourced from recycled data on amount of batteries put on the batteries. Some of the lead recycled from market during the years by every producer batteries in the informal sector, however, / importer. Every producer / importer can does not re-enter the manufacturing sector calculate his market share that is a base for but is used instead for other purposes, such calculation of the collection share. as sinkers for fishing lines. The producer / importer is also obliged to The costs of used lead batteries treatment fulfil recycling and recovery limits. He must and recovery vary according to the market cooperate also with the facilities dealing situation. It is impossible to make estimation Fig. 47: Scheme of waste, finance and information streams in used lead batteries EPR system with the treatment and recovery of used of the costs because prices in Europe are

72 73 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

Therefore, a specific contextual map should Conclusions and operate treatment in the same facility and in appropriate distance (best of all in the be generated, encompassing local politics, recommendations technology as recycling by metallurgical country or in a not-very-far distance in economical aspects, social aspects, local technologies but it is not the necessary neighbouring countries), and international market aspects, etc., As the lead batteries are at once an condition. The treatment means dismantling 4. effective state control and supervision and the lead recycling plant inserted into important source of secondary lead and of used lead batteries in order to get metals to prevent human health and this context. No solutions or orientations environmental danger it is necessary to and other components. It is recommended environmental hazard together with given here should be taken for granted but, operate efficient system for environmentally to respect European standards for used good law enforcement. instead, analyzed under the lights of this sound management of used lead batteries lead batteries treatment given by BREF contextual map and its possibilities. in the countries. The very effective model for documents, mainly given by BREF on Non- used batteries is implemented in European Ferrous Metals7. European standards also Union based on extended producer cover the best available techniques for lead responsibility. This model generalise recycling. sufficient financial sources that can cover all Some wastes arisen during the processes costs of separate collection, treatment and of treatment and recycling cannot be recycling of used lead batteries. This is the recovered and they must be landfilled on main assumption for building an effective special landfills for hazardous wastes. The system. technical and environmental conditions The first and the most important step of for landfilling of hazardous wastes are also used lead batteries management is separate introduced. collection. It is obvious that throwing The necessary part of all steps of waste away the used lead batteries together with management is transport. As lead batteries mixed household waste is wasting material (new or used) are hazardous and introduce resources and could lead to the potential danger especially for waters (surface burden of the environment and public or underground) special conditions for health. It is recommended to collect used transport must be followed. batteries in places of their production, i.e. The system of environmental sound in services and maintenance operations. management of used lead batteries can be Effective system is mobile collection successfully implemented only when four when mostly batteries from households conditions is met: and very small operations are collected. 1. legislative rules are effective and There are also other collection systems applicable, available for used batteries collection.The 2. all or at least most of producers / efficiency of secondary lead production is importers of lead batteries are depended on the sorting and treatment of participating in the system, used lead batteries. It is recommended to 3. facilities for lead recycling are available

74 75 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

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1. Secretariat of the Basel Convention: for the Non-Ferrous Metals Industries. 12. European Commission – European 16. Slovák Ľ.: The present forms and Technical Guidelines for the Draft3 February 2013. http://eippcb.jrc. Integrated Pollution Prevention methods of processing of portable Environmentally Sound Management ec.europa.eu/reference/ and Control Bureau: Best Available batteries in the Slovak Republic. Havlík of Waste Lead-acid Batteries. Basel Techniques (BAT) Reference Document T., Demeter P. (editors): Recycling of Used Convention Series/SBC No. 2003/9, 2003, 8. European Commission: Questions and for Iron and Steel Production. Industrial Portable batteries and accumulators, http://archive.basel.int/pub/techguid/ answers on the batteries Directive. Emissions Directive 2010/75/EU Sklené Teplice 2009 tech-wasteacid. Commission Services Document - not (Integrated Pollution Prevention and legally binding, last updated in March Control), adopted March 2012. http:// 17. www.geomat.sk 2. Secretariat of the Basel Convention: 2011. Brussels. http://ec.europa.eu/ eippcb.jrc.ec.europa.eu/reference/ Environmentally Sound Management of environment/waste/batteries/pdf/qa.pdf 18. Regulation (EC) No 1013/2006 of the Lead Batteries in Syrian Arab Republic: 13. European Commission – European European Parliament and the Council of Proposals for policy reforms. Basel 9. Directive 2006/66/EC of the European Integrated Pollution Prevention and 14 June 2006 on shipment of waste Convention, October 2011 Parliament and of the Council of 6 Control Bureau (2006b): Reference September 2006 on batteries and Document on Best Available Techniques 19. UNECE – United Nations Economic 3. http://www.who.int accumulators and waste batteries and for the Waste Treatment Industries. Commission for Europe: ADR - European accumulators and repealing Directive August 2006. http://eippcb.jrc.ec.europa. Agreement concerning the International 4. http://batteryuniversity.com/learn/ 91/157/EEC eu/reference/ Carriage of Dangerous Goods by Road. article/health_concerns Geneva, . http://www.unece. 10. European Commission – European 14. European Commission – European org/fileadmin/DAM/trans/danger/publi/ 5. www.eurobat.org Integrated Pollution Prevention and Integrated Pollution Prevention and adr/adr2011/English/VolumeII.pdf Control Bureau: Reference Document on Control Bureau: Reference Document on 6. Planet Ark Research Report: Lead acid Best Available Techniques on Emissions Best Available Techniques in Smitheries 20. Convention concerning International battery use, disposal & recycling in from Storage. July 2006. http://eippcb. and Foundries Industry. May 2005. Carriage by Rail (COTIF) of 9 May 1980, Australia. Data provided by Australian jrc.ec.europa.eu/reference/ http://eippcb.jrc.ec.europa.eu/reference/ as amended by the Vilnius Protocol of 3 Battery Recycling Initiative in 2010. June 1999 Australia. (http://recyclingweek. 11. European Commission – European 15. ESWI - Expert Team to Support planetark.org/documents/doc-687-lab- Integrated Pollution Prevention and Waste Implementation: Study on the 21. European Commission (2012): Batteries. report-2011-11-09-final.pdf) Control Bureau: Reference Document calculation of recycling efficiencies and Brussels. http://ec.europa.eu/ on Best Available Techniques in the Non implementation of export article (Art. environment/waste/batteries/index.htm. 7. European Commission – European Ferrous Metals Industries. December 15) of the Batteries Directive 2006/66/ accessed June 2012 Integrated Pollution Prevention and 2001. http://eippcb.jrc.ec.europa.eu/ EC. Study on behalf of the European Control Bureau: Draft Reference reference/ Commission, Brussels, Final Report, May 22. UNECE – United Nations Economic Document on Best Available Techniques 2009 Commission for Europe (2001): UN

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Recommendations on the Transport of 28. http://en.wikipedia.org/wiki/ Dangerous Goods - Model Regulations. Reverberatory_furnace Geneva, Switzerland. http://www.unece. org/trans/danger/publi/unrec/12_e. 29. http://en.wikipedia.org/wiki/Blast_ furnace 23. http://www.lead-battery-recycling.com/ Used-battery-recycling.html 30. http://en.wikipedia.org/wiki/Rotary_kiln

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25. Brian Wilson - ILMC, Implementing Regional ULAB Recycling Strategies for Central America, Venezuela, Colombia and the Caribbean, Impacts and Consequences, San Salvador, El Salvador, May 2013, http://www.itu.int/en/ITU-T/ climatechange/201303/Pages/default.aspx

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78 79 Environmentally Sound Management of Used Lead Batteries in the Mediterranean

United Nations Environment Programme Coordinating Unit for the Mediterranean Action Plan Barcelona Convention Secretariat

Vassileos Konstantinou 48, Athens 11635, Greece Tel.: +30 210 7273100 – Fax: +30 210 7253196 www.unepmap.org ISBN: 978-92-807-3520-8

United Nations Environment Programme Coordinating Unit for the Mediterranean Action Plan Barcelona Convention Secretariat

Vassileos Konstantinou 48, Athens 11635, Greece Tel.: +30 210 7273100 – Fax: +30 210 7253196 www.unepmap.org