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Environmental and

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Lead-Acid

BaDen Recvcling

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1 A Workbook for Trainers 1

First Edition .April 1996

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S.""', \~ iF~UNEPUNITED NATIONS ENVIRONMENT PROGRAMMElNDUSTRY AND ENVIRONMENT

39-43, QUAI ANDRE CITROEN75739 PARIS CEDEX 15 -FRANCE

TEL: (33)0144371450FAX: (33) 0144 371474E-MAIL : [email protected]

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UNEP Training Unit A Workbookfor TrainersThis workbook is one of a series that provides practical support mate rial toteachers and trainers wishing to commence or enrich their curriculum withup-to-date approaches in environmental management.

It is based on extended experience with training workshops by UNEP andailier agencies, and is now being made available for wider use in allregions throughout the world.

ACknOWled~emen~s " .')The first version of thls tramers workbook was prepared m

1994 by J.W. Scheijgrond and F. Balkau forUNEP lE.

It was subsequently trialled in workshops and courses in

several places, leading to subsequent revisions to produce

this current document.

UNEP would like to thank the many individuals andorganizations who contributed ideas and materials, or whoassisted in reviews and redrafting. Particular thanks go toMr H. Ahmadzai, Mr R. Boehnke, Mr J. Delcambre, Mr J. Hay,Mr M. Hyman, Mr M. Ichimura. the International Lead ZincOrganization Inc., Metaleurop (Mr P. Fossi, Mr P. David, andMs E. Perrier), and Mr A. Tay.

Copyright @ UNEP 1996Ali rights reserved. No part ofthis publication may be produced, stored in .a retrieval system or transmitted in any form or any means: electronic, )electrostatic, magnetic tape, mechanical, photocopying, recording or .'

otherwise, without permission in writing from the copyright holder.

First edition April 1996

The designations employed and the presentation of the material in thispublication do not imply the expression of any opinion whatsoever on thepart of the United Nations Environment Programme conceming the legalstatus of any country, territory, city or area or of ilS authorities, orconceming dei imitation of its frontiers or boundaries. Moreover, theviews expressed do not necessarily represent the decision or the statedpolicy of the United Nations Environment Programme, nor does citing oftrade names or commercial processes constitute endorsement.

United Hations Publication

1 ISBN 92-807-1611-5 1

.)

8Table 01 Contents

Environmental and Technological Issuesrelated to Lead-Acid Battery Recycling

Evaluation Form iUsers Guide iiiGlossary v

Part 1 Introduction

1.1 This package 1:4

1.2 Contents ofthis package 1:5

8 Part Il Organizing E~ective Training Activities2.1 Introduction 11:3

2.2 Notes on interactive workshop organizatioll 11:4

2.3 Some ideas for more effective communication II:52.4 Some personal suggestions for effective .training II:62.5 Resource persons guide II:1

2.6 Suggestions for self study II:9

Part III Technical Background Papers3.1 Introduction III:3

3.2 Introductory articles III:5

3.3 The recycling scheme oflead-acid batteries 111:113.4 Secondary lead smelting III:25

3.5 Transparencies , III:51

Part IV Information Sources4.1 Introduction IV:3

4.2 Sources of information IV:3

8 4.3 Documents on lead ~d lead-acid batteries rec:cling IV:54.4 Handbooks on chemlcals, humans and the envlronment IV:14.5 Audiovisuals , IV:8

4.6 Some useful background documents on the environment IV: 10

Part V Training Material5.1 Introduction V:3

5.2 Some ideas for training activities V:4

5.3 Some ideas for preliminary exercises """"""""""""""'."""""""""""' V:6

5.4 Work exercises V:8

5.5 Answers to the work exercises V:40

Appendices1 Supporting Documents for this Package , 3

Il List of Training Resource Packages availablefrom UNEP IE 5

/II About UNEP lndustry and Environment , 7

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8Users Guide

T his is a train ers support package, not a problem-solving. Such work needs to be guided

reference book. It does Dot give a by a tutor who is a recognized expert in the field.

systematic, comprehensive overview This method allows the full complexity of real

(there is Dot enough room to do fuis); rather, it decision-making to be explored.

focuses on some selected aspects that are central Where calculations are required, they are more

to the subject. The structure of the document oriented towards throwing light on useful

allows further sections to be easily developed and approaches or management decisions than simply

added as additional modules. finding the 'correct' answer. Trainers are

The package is written for trainers to provide strongly urged DOt to see ibis package merely as

them with support material and ideas, rather than a set of arithmetic exercises.

8 as a study book for students. The average trainee ln some instances, answers are indicated. For

will only ever see a few pages or exercises many problems, the 'correct' answer depends on

reproduced from ibis document. the context of the question. It is here that a tutor

One of the purposes ofthis package is to provide or extemal resource expert is useful.

some case studies and situation scenarios that can Many trainers fmd this disturbing. They should

be used as a basis for interactive training and remember that real decision-making depends on

simulated decision-making. However, the the wider circumstances surrounding the

exercises only explore a small part of the potential problem, and that a numerical answer which is

of the case studies, and trainers are strongly politically or socially unacceptable, or

encouraged to develop further exercises or tasks. administratively unworkable (even though

The package is oriented at developing insights accurate), is DOt in effect 'correct'.

and decision-making skills. For teaching the The simulation ofreallife situations and

factual knowledge base of the subject, train ers are decision-making that is the basis ofthis package

referred to the reading lists in the bibliography. makes it most suitable for senior students and

Work exercises are predominantly based on trainees, and especially for professional training

interactive groupwork and a team approach to (or retraining) courses.

8Do not forget to refer also to the package on Cleaner Production for teaching the underlying concepts

and approaches in ibis workbook.

F inally, we must stress again that ibis package does DOt cover aIl aspects of the subject.

Its prime purpose is to lead trainers into ibis field, and to help and encourage them to develop

their own material, appropriately tailored to their specific leaming situation. UNEP is prepared to work

further with trainers who wish to extend ibis package into new directions, or go into greater depths

on some subjects.

8

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iv United Nations Environment Programme' Industry and Environment

How to stan a training activitv )

based on this workbook

1 Remember tl,at this is a starters kit, not a 3 Refresh your memory by reading some of the

complete recipe book. Remember also that the background papers and studying the overhead

workbook aims to develop insights and decision- transparencies. Write rOUf own notes in the

making skills, not to convey knowledge or facts. spaces provided.

This is the task of the references listed separately. 4 IdentifY some expert resource persons who

2 Understand the needs ofyour trainees. What could be invited as rotors to help you in

insights or ski Ils do you intend to develop? discussion sessions.

Defme rOUf learning objectives.

5 Select some ~f tl,e exercises you wish to 7 DeveloP other exercises or questions ')

present to tramees. yourself.

6 Examine carefully the case study or 8 Develop your own local case study ifyou can,

scenario on which they are based. Be sure and use this instead of the one in the pac}<age.

that you have at least one solution to the exercise 9 prepare some background questions and

that you can explain and defend. preliminary exercises for trainees to carry out

before they start the workshop/course.

1 Q In session, summarize tl,e issues for a rotor. Discuss and compare results. Be open

trainees using the overheads given, and to ideas and experiences from trainees, and

others you may have. Discuss the problems and discuss these.

difficulties decision-makers face. Discuss where 12 Return to tl,e learning objectives, and

factual information can be found to help in check that they have been achieved.

decision-making. 13 Consider how to fo/low up and reinforce

Il Commence the work sessions, preferably the learning experience by establishing

in small groups, and preferably guided by some ongoing projects, or periodic reunions.

)Refer also to otl,er packages and workbooks, wl,ere useful additional teaching material is found.

To facilitate using this workbook, the header of odd-numbered pages describes the contents of that

particular section. This information is also repeated in the footer of even-numbered pages. You can crack

rOUf progress through the workbook by referring to the calibrations on the bar across the bottom of odd-

numbered pages:

The shading shows your current position in the text.

)Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers

v

eGlossarv

This glossary contains some of the tenns round in the background papers or in other papersconceming lead-acid battery recycling. This glossary is Dot complete and you may want to add

further items.

The fol/owing sources have been used: Environment Canada, UNEP lE, Greenpeace, and TheEnvironmental Glossary (D. Dooley, K. Patrick)

APELL Awareness and Preparedness for Emergencies performing with the aim of helping to safeguard the

at a Local Level. environment by: (i) facilitating management contraI ofBag filter Name of a type of filter used for extracting environmental practices; and (ii) assessing compliance

airbome dust from the atrnosphere. with company policies, which would includee Basel Convention The Basel Convention on the regulatory requirements.

Control ofTransboundary Movements of Hazardous Environmental impact assessment An analysis toWastes and their Disposai (1989) aims to contraI the determine whether an action or project wouldtransboundary movement and disposaI ofhazardous significantly affect the environrnent.wastes. Good housekeeping Efficient management of the

Battery breaker A preliminary processor of batteries property and equipment of an institution orthat applies a variety of techniques to break the organization. ln the context of cleaner production, it

battery, drain the sulphuric acid from the battery often refers to the procedures applied in the operation

cavity, remove plastic and sell the lead components to of a production process.the smelter. Battery breakers may be independent Grid Metallic grille-like structural framework in abusinesses or encompassed in secondary smelting battery. Its purpose is to support the active materialoperations. and conduct current to the cell terminais. It is cast

Cleaner production The continuous application of from a high purity lead alloyed with approximatelyan integrated preventive strategy to processes and 5% to 12% antimony, 0.5% tin, and a few hundredthsproducts, in order to reduce environmental risks peT cent of coppeT and arsenic.and impacts. Heavy metals Metallic elements with high atomic

Cradle-to-grave The life cycle of a product, from weights, e.g. mercury, chromium, cadmium, arsenic,e raw material to final disposaI. and lead.Dross By-product which is formed during refining. Ingotting Solidifying of lead in molds after refining.

Chemical compounds added during refining form Lead bu Ilion The liquid lead, still containingdrosses, which usually float on the molten surface. impurities, which is formed in the smelter.Apart from lead, drosses contain impurities such as Life cycle The combination ofprocesses needed by acopper. nickel, and antimony. product to fulfil the function specified by the

Emission An emission usually refers to fugitive or functional unit. Life cycle stages include production,waste discharges from a process. Emissions are use and processing after disposai, including the

traditionally associated with atrnospheric discharges. processing of the waste generated in these stages.End-of-pipe treatment Treating pollutants at the end Life cycle analysis A quantitative assessment of the

of a process (by, for example, filters, catalysts and total environmental impacts caused by a particularscrubbers) instead of preventing their occurrence. process or product, from resource consumption to

Environmental auditing The management tool contamination, from the cradle to the grave.comprising a systematic, documented, periodic and Mass/Material balance A precise account of aIl theobjective evaluation of how weIl environmental inputs and outputs of a process, based on the law of

organization, management and equipment are conservation of mass.

e "c "A Workbookfor Tralners":Environmental and Technologicallssues related to Lead-Acid Battery Recyclmg

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vi United Nations Environment Programme' Industry and Environment

Matte Molten material in the course of the recovery entrained or absorbed in the water and ",)

process in a smelter: it is not completely pure metal so easily controlled.and requires further processing. Secondary lead Lead which bas been used for

Ore A mixture of mineraIs and a gangue from which at different applications for which it bas no longer hasleast one of the mineraIs can be extracted at a profit. a purpose, and which is to be recycled.

Paste The mixture of lead oxide and lead sulphate, Secondary lead smelter The metallurgical processoriginating from the lead-acid batteries. that remelts or refines lead ingots, or lead-containing

Pollution The term describes the presence ofharmful, scrap ofvarious types, and produces lead compoundhazardous or detrimental constituents in an which is further processed.environment. A polluted environment describes astate Separator PVC plates functioning as isolators to keepthat occurs when the assimilative capacity of the the anode and the cathode from direct electricalenvironment is exceeded, resulting in undesirable contact. It is porous enough to retain sulphuric acid

ecological changes. and allow electric current to flow between the plates.Primary lead purification Originating from ores or Slag Sol id waste produced from a metallurgical

concentrates. High temperature process where lead fumace. It is predominantly non-metallicoxide drosses are reduced to metallic lead and in composition.impurities, such as iron, arsenic, antimony, and SU battery Starting Lighting and Ignition batteries. ...tin are removed in slags. They are used in cars, trucks, and buses. :)

Raw material A material on which a particular Smelting The partial recovery of metal in molten form.manufacturing process is carried out. Smelting is required to recover the metal content and

Reclamation recycling The recovery ofuseful convert it to a form that is ready for refining.products from waste materials. The retrieval of Sustainable development Meeting the needs of the

materials or products for re-use in their original form present generation without compromising the abilityor for reprocessing into other products. of future generations to meet their needs.

Recovery The extraction of material from waste that Sweating The process where the molten lead ismay be recycled or reused. Recovery may take place separated from the various types of scrap containingat the source ofwaste production or as a process both metallic and non-metallic impurities. The processduring waste handling. is executed in a reverberatory fumace.

Refining Removing ofmetals which are not desired in Technology assessment A study or evaluation tothe end product by adding reactants which form help understand the likely impact of the use of a newdrosses with the unwanted metals. The drosses are technology by an industry or society.then skimmed off. Used lead-acid battery A lead-acid battery that bas

Reuse Retrieval of material or products for its original been taken out of service because it is spent, due topurpose within the same site. ln case of lead.acid temporary battery failure, discharge, car scrapping,batteries: ensuring that no battery is taken out of etc. Used lead-acid batteries present an environmental "

service until it can no longer be serviced and used. and health threat when improperly disposed due .,";

Reuse efforts presently focus on reconditioning and to corrosiveness and potential toxicity of

recharging batteries to extend their usefullife. component parts.Scrap Discarded material from manufacturing or Wrecking The process during which the battery is

processing or remnants after an article's usefullife bas crushed into smaller fractions. The sulphuric acid isfUn out. Lead scrap is of three types: whole battery separated first after which, optionally, the crushedscrap, industrial scrap (such as drosses), and other battery can be separated into the following fractions:scrap (such as cable sheathings). lead grids, lead paste, polypropylene, PVC,

Scrubber Device for flue gas cleaning. If dust and gas and ebonite.

coli ide or contact with water, they will become

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers

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Part 1

Introductioni

( 1.1 This package 1:4

1.2 Contents of this package 1:5

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8

1 Introduction

M any teaching institutions and ln 1993, in response to these findings, UNEP,individual train ers have difficulty in WHO, and ILO jointly initiated the programmefollowing the rapid evolution of on Training Approaches for Environmental

environmental issues that are relevant to their Management in lndustry. The programme airns tocourses. enhance the capacity of national institutions to

This is particularly true when teaching subjects offer local training on topics concerned with the8 such as pollution and environmental manage- prevention of industrial pollution.

ment. And yet it is important that new graduates ln this context, trainers' packages have beenhave a good knowledge of issues in which they prepared on different areas of environmental

may eventually provide consulting services or management. These packages are intended topolicy advice to governments and industry. help educators and trainers to develop their own

The fact that development and environment are workshops or curricula, or to integrate some ofinterrelated means that it is more vital than ever the ideas and infonnation into aIready existingthat: teaching programmes.

.ail professionals have a basic environmental It is important to keep in mind thatliteracy that helps them to incorporate these training resource packages merelyenvironmental priorities into their specialized pro vide afirst orientation to the topic.work, whatever their profession;

.specialized environmental courses are relevant ln no way does the package constituteto today 's environmental agenda. a 'course' in its own right.

8

8"'"'"'"'"'"'"'c""'AWorkbookfOr Trainers : Environmental and Technologicallssues related to Lead-Acld Battery Recycllng

1:4 United Nations Environment Programme' Industry and Environment

1.1 This package ')

This package is a workbook that complements balanced curriculum in response to the needs ofthe trainer's package on 'C/eaner his/her audience. Any missing elements may be

Production '. For best results, both should be used found in one of the other UNEP manuals, to betogether. ln many cases, it would be useful to use converted into training format based on the casethe C/eaner Production material as an studies and scenario included here.introduction to any curriculum-based material in Thus, the package is Dot static.fuis workbook. As feedback is received from users and

The workbook is balanced between curriculum- technical specialists, the material will bebased content (useful for technicians) and a more modified and enriched.management systems approach (useful for Users are encouraged to report on theirsupervisors and managers). ln practice, both will experiences in using fuis package, and to send inbe needed, and the trainer is urged to develop a suggestions for improvements.

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T he package focuses on the environmental how environmental problems related to recyclingaspects of product recycling. It uses battery can occur and be solved.

recycling to illustrate that product recycling can, This training resource package considers theif precautions are not taken, cause serious technologies of recycling the various constituentsenvironmental and health problems. The reasons of the lead-acid battery. We refer to thesewhy it has been selected for this training resource technologies as secondary /ead sme/ters. Healthpackage are that: and safety, pollution control, and environmental.recycling of lead-acid batteries and lead scrap impact are integrated in fuis consideration.

bas a history going back to the last century, and lt is during secondary lead smelting that theis weIl understood. most serious environmental problems occur. The

.compared to other recycling loops, the background papers discuss various secondaryrecycling of lead-acid batteries is fairly simple lead smelting technologies, and the exercises inand effective. ln many countries, more than Part 5 also focus mainly on these technologies.90% of alllead-acid batteries are recycled. ln the context of fuis package. it is impossible

.although recycling is often regarded as being to include aIl the information on lead-acid batteryautomatically environmentally friendly, this is recycling technologies. Due to increasing ;-

DOt always crue. Lead-acid battery smelting pressure forcing (secondary) lead-smelters toconfirms this. Smelting and refining of lead- comply with stringent environmental standards,acid batteries involve considerable risks for many developments are going on in fuis field,humans and the environment when no adequate and many new technologies are emerging.pollution control measures are provided. UNEP lE plans to publish in 1996/97 aHowever, simple disposai of batteries also technical report that gives a more comprehensiveposes serious problems for the environment. and systematic overview. The trainer may thusLead-acid battery recycling functions as a want to update this package from rime to time.

use fui role-model for recycling practices in this Part 4 gives some addresses where updates ontraining resource package. the latest technologies can be found.

This role-model function (and its associated The package is suitable for a wide range ofenvironmental problems) can be used as an audiences who do not necessarily need aexample of how a recycling scheme is set up, and technical background in order to be able to

understand the suggested reading and undertake


Part 1 .Introduction

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8 the exercises in Part 50 The package can also be Ali parts of the package can be used for

used to prepare a presentation on lead-acid preparing such a workshop, although some of thebattery recycling and its environmental impacts. exercises may be time consumingoThe background readings and the transparencies Thirdly, the package can function as a resourceprovide the necessary information for fuis for teachers to include the topic in existingpurposeo It gives the trainer enough background curricula for undergraduate students who have amaterial and tools to prepare a three to four technical background. Part 4 of the package canhour workshopo be especially useful for fuis purposeo

"' 12 Contents of tbis package8

T his package is conceived principally to help .supplementary technica/ information to supporttrainers prepare a seminar, workshop, or some work exercises;

extended course. It is not a course per se. .work exercises and questions;The package contains: .appendices with further information about

.suggestions and hints for effective training; UNEP and its programmes..a short backgroundto the subject, drawn from Trainers are encouraged to extend the package

other existing publications; by adding their own case studies and exercises,.overhead transparencies to introduce and and expanding the subject coverage into new

illustrate the main ideas; topics. For example, train ers in environmental.case studies and situation reports and scenarios health may wish to add some modules on

drawn from actual experience; occupational safety and ecotoxicity by buildingon the chemical information already presentedo

8

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Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkboak for Trainers

Part 1 .Introduction

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Part 2

Organizing Enectiver Training Activities

2.1 Introduction Il:3

2.2 Notes on interactive workshop organization Il:4

<. 2.3 Some ideas for more effective communication Il:5

2.4 Some personal suggestions for effective training 11:6

2.5 Resource persons guide , Il:7

2.6 Suggestions for self study 11:9

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Il:3

82 Organizing EUective

Training Activities

2.1 Introduction

C ommunication and organizational ski Ils Accordingly, this package relies on interactive8 are just as important as a technical teaching methods, using working exercises, case

appreciation of the subject. Professional studies, and groupwork problem-solving, rathereducators already understand this point, but than on lecture format.teaching is a very individual matter, and Interactive techniques are more complex tointeractive teaching can be very demanding on a organize than simple lecture-giving, but they givebusy person. better results. ln particular, interactive methods

Here, we recall some of the key aspects of the are more likely to provide students with practicalleaming process. skills. This is important where skill development

This text contains suggestions about: rather than factual knowledge is the objective..how to ensure maximum effectiveness as a Lectures are better at providing factual

trainer knowledge than at developing skills..how to organize effective training activities and For example, a workshop format is verypresentations. effective in providing training on the effectiveWe have provided this advice before use of management tools such as Environmental

consideration of the technical material, so that Impact Assessment (ElA), or audits. For highreaders can remind themselves of the importance level environmental management, bothof the advice when choosing work exercises and knowledge and skills are required, so the8 training projects, later in this package. appropriate mixture of techniques should be used.

The notes in this Part are based on theAdults learn best wllen tlley are act;vely experiences ofUNEP lE and WHO in organizing

engaged. They remember 20% of what they hear, workshops and other training sessions.40% ofwhat they see and 80% ofwhat they Personal advice on how to be an effective trainerd. fi th 1 ' is also given by several experienced trainers, who

lscover or emse ves.aIl use interactive training approaches.

8 cc """'AWorkbookforTrainers:Ènvironmentai and Technological Issues related to Lead-Acid Battery Recycllng

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2.2 Notes on interactive workshop organization .)

2.2.1 Workshops

W orkshoPs provide a stimulating leaming .preparation of a country report by eachenvironment where people with a wide participant before the workshop

range of experiences and skills can join together .short introductory or overview lectures on keyto address practical problems beyond the ability issuesof an individual to resolve. .practical problem-solving work exercises on

Interactive workshops use a combination of case studiesseveral techniques to bring about a deeper and .feedback by experts and discussions onmore pragmatic leaming experience than is workshop exercisespossible with a lecture-style format. .panel sessions (that is, question-answer

Workshops also provide excellent opportunities dialogues) with expertsfor exchanging personal experiences, problem- .individual study sessions, computer quizzes,solving through panel sessions and direct and so on.consultations with experts, and discussing some .structured oral presentations of country reports ._~)of the complex situations which surround most leading to a regional overview "

environmental problems. .audiovisuals such as videos, films, and slidesThe UNEP/WHO workshop format .field visits where appropriate

incorporates the following elements: .personal action planning by participants for

.sending out pre-workshop reading material, follow-up activity.with some simple exercises

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2.2.2 Preparation

Sessions need to be carefully prepared, withparticipants knowing in advance what they It cannot be overstressed how important it is

will do or see. A proforma report form for that participants should be thoroughly preparedcountry reports gives a common format to these for the workshops, and tllat ail tl,e pre-sessions. Country reports should also try to link workshop activities I,ave been completed.the issues with other sessions.~~---C=~_L

2.2.3 Organization ..~)

T he organization ofworking group sessions The foie ofresource experts as advisors isalso requires care. Groups should first meet crucial. They should have sufficient experience to

informally, elect their own chairman, and then act assist in aIl sessions and provide general adviceas a permanent team in various workshop on ail subjects in workshops, discussion or panelsessions. They are guided, but not instructed, by sessions. They should not, however, dominate the

technical experts. workshops.It is use fui to finish the workshop by preparing The five clay format is ideal for covering ail

personal action plans. Participants should develop these requirements. If less than five days is taken,and present their proposais for what they can you can be sure that important issues will be leftinitiate immediately on their retum home. Such out. If more time is available, consider includingaction includes: social events and private study sessions, along.what they can achieve unassisted, and with more extensive project work for the.what else they could achieve if some assistance students.

were available.

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers ).

Part 2 .Organizing Effective Training Activities

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82.3 Some ideas lor more enective communication

I f the training is to be successful, effective .trainees who are traditionally used to lecturescommunication is essential- from recognition are suddenly required to take part in discussion

of the training need to the final evaluation of the groups, which might feel alien to them.event. Most of the se issues can be anticipated and

Without good communication, aIl manDer of overcome by good communication between thethings can go wrong: course designers, writers, and event organizers.the training is too early -or too late -to make and presenters on the one side, and the students

any impact on performance and their organizations on the other..trainees do not know what the training is about Some simple communication considerations will

or what to expect help to improve outputs in training and avoid.the course is planned for a local public holiday disasters.

8 Before the learning eventFind out:.how the leamers have been taught in the past.the real needs and situation of the leamers.whether the facilities are adequate for the envisaged training.whether the training has the support of senior people.how success will be measured.

Make a project plan for the organizers, giving details of howthe event will be organized. Send the plan ta them. with detailsof the key dates and needs.

During the learning.find out how relevant the topics are to the work situation of the

participants.start with the familiar ail can -not a video of an ail

spill disaster.communicate using topics, themes and issues inthe

local press8 .store unanswered questions, and remember to answer

them before the end.keep notes for participants to bullet-point fonnat.ensure the participants keep notes for future reference -few

read essays, or even articles.if you are working in a foreign language, at least translate the

si ides.

After the learning event.always communicate your thanks and best wishes.infonn participants on follow-up study procedures, and how the

instructor can help to analyze the evaluations and infonn theorganizers of the results

.communicate to colleagues the results of the training and whatcan be leamed from these results.

8Issues related to Lead-Acid Battery Recycling


2A Some personal suggestions ')

for enective training

T he following suggestions corne from four teachers with long experience in training. They are ail

different in character, and therefore in teaching approaches. However, they ail believe in an

enthusiasm for the subject which is critical when teaching students.

To be an effective educator/teacher: The outstanding educatorlteacher:

.Provide an enjoyable learning situation that expands .Is fully acquainted with, and believes in, the

ail of the participants' network. educational merit of the subject matter.

.Model courses and teaching styles on examples that .Utilizes clear and graphic illustrations to inform '": you think are outstanding. Ask yourself about the and motivate the students to learn. )

qualities of a good instructor or a good course, and .Utilizes learning approaches including multi-

follow the answers you corne up with. media, projects, interviews, questionnaires,

.Allow the subject matter to be discussed and debates, and similar interactive approaches to

discovered by students -not hammered in. ensure full involvement of the students.

.Make courses relevant and interesting by .Reacts positively to aIl questions -there are no

understanding your audience. Ask them what they Stupid Questions, only Stupid Answers.

already know, and then plan for their needs. .Remembers that positive reinforcement is a

Incorporate ideas from the group in the course. better motivational approach than criticism.

.Remember that no amount of style will substitute for .Is available for private discussions with

a lack of substance. individual students or groups of students.

Deborah Hanlon, Environmental Scientist Don Huisingh, Environmental Consultant and Professor at

Office of Environmental Engineering Erasmus University in Rotterdam

and Technology Demonstration, US EPA the Netherlands

To be efficient ('doing things right'), and The best educator/teacher:

effective ('doing the right things:J: .Likes the learners, and has a true understanding of

.Think about helping people to learn, rather than how they learn.

teaching them. .Has the ability to communicate. ).Seek learner feedback, and measure learning .Will change the training programme and the ",

achieved with objective tests. approach if necessary.

.Set learning lime limits. .Is stililearning, and has recent applied experience of

.Seek conscious and unconscious leaming. the subject being taught.

.Seek learning that endures, based on .Has the ability to organise events and to manage

understanding and skills. things.Bob Boland, Environmental Consultant, France Colin Sutherland, Educational Consultant, Franœ

;~Environmental and Technologicallssues related to Lead.Acid Battery Recycling : A Workbook for Trainers )


_..". .., ~

frIt Il:7

8 2.5 Resource persons guide

A s this package relies heavily on interactive groupwork sessions, here are some guidelines on howto be an effective resource person.

ln a case study-based training approach, the resource person serves more as a:.facilitator of the group leaming process

.technical adviser as needed,and a.catalyst of leaming

rather than a:.lecturer

.story-telleror

.instructor.

8Here are some guidelines on how to be an effective resource person.

1Be sure that you have read and understood and respective organizations, etc., whichthoroughly the participant's notes before you should have been done on the first day anyway.

meet your group. There's nothing like being .then ask if the objectives and purpose of theprepared and more familiar with the case study exercise, which have been previously discussedscenario than the participants are! in the plenary session, are clear to them.2Before every group work session, take time Sample objectives are:

to visit your assigned meeting room and -identify and understand the options that SMEscheck the: can employ in their pollution prevention.seating arrangements There should be a large program

enough table surrounded by enough chairs for -evaluate the feasibility and suitability ofthesethe participants and yourself options in view oftechnical, environmental,

.equipment and supplies such as flipcharts, financial, organizational, and social criteriaflipchart papers, markeT pens, whitelblack and constraints.

8 board, board eraser, masking tape, transparency It will be useful to know whether the majoritysheets, writing pads, ballpen/pencils, calculator, of the group members have actually read the textetc. provided, which states the background and the

.physical conditions of the room There should problem.be sufficient lighting, the room temperature Ifthey have Dot, then you will need to directshould be comfortable, noise should be as low them to focus their attention first on what needsas possible, etc. to be accomplished by the end of each part.3During the initial group meeting, it is 4IfYOUr group gets involved in.diverse issues,

important to set an informai andfriendly try to steer them back on the nght track byatmosphere. It is suggested that you: asking relevant questions, rather than telling.introduce yourselj; preferably asking everyone them what to do.

to cali you by your first name, and then let 5Give technical assistance andeverybody introduce himself/herself in a similar supplementary information as needed,

manner. Do not waste rime stating positions

8Recycling

_c ~ ,""'


without 'spoon-feeding' the participants. persons need to be duly advised on the ")However, do Dot lecture or dominate the group particular question.discussion process. 9see to it that you compare notes, exchange6AlthOUgh you need Dot star with rOUf group hints, and share strategies with other

for 100% of the lime, it is expected that you: resource persons so that you can assist one.spend at least 80% afthe time with them during another, as weil as gauge rOUf group's progress

regular sessions. The crucial times are at the in comparison with the others.beginning, middle, and near the endofeach 1OIftension or heated argument arisesgroupwork session. arnong your group members, try rOUf

.Ifthey decide to work beyond the prescribed best (with a sense ofhumor) to defuse it.regular time, just make sure that they are on the Il ln the case of absenteeism, approach theright track; your presence during overtime is person/persons in question and encouragenot mandatory, but voluntary. them to participate.7There will be critical parts during the 12 If one or two group members are

identification of options, followed by dominating the discussions or doing ailtechnical, environmental, and economic the work, intervene and encourage everyone toevaluation, where rOUf technical advice will be cet involved. ln order to do fuis effectively, you .,~

)most needed by rOUf group. need to be attuned to rOUf group's 'culture' andThe best way to assist the participants is by trend of discussion.

giving only the advantages and disadvantages of 13Although division of labor is a limethe options in question. Let them weigh these saving group work strategy, you mustpros and cons and decide for themselves whether ensure that it is DOt done to the extent that there isto take or drop the option. no peer learning and discussion occurring. It is8 Ifyou encounter any question about the counter-productive for group members to work

technical content of the material that you individually on these exercises.have not been briefed on, discuss it with the 14The most productive, meaningful andTeam Leader and agree on how to tackle tl,e fulfilling group work is when they gel tosituation. It may weil be that the other resource accomplish what they have to do as a team -and

have fun in the process!

J

Environmental and Technologicallssues related to Lead-Acid Battery Recycling: A Warkbaak for Trainers ...:,,)


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8 2.6 Suggestions for self studv

A lthOUgh this package was designed supplemented by further reading and additionalto provide resources for trainers, training materials listed in the Appendices, andthe potential for self-study should perhaps by site visits and discussions with

not be ignored. professionals.The package does not constitute a complete The following approach is suggested for

course on cleaner production in leather tanning, individual study.but can be seen as an introduction to be

8 .Read the introduction, but avoid any sections on organizing training events.

.Seek out the section containing background papers or subject content. Read throughthe whole section as narrative.

.Work through the pages offered to the trainer for overhead projection, and ensureyou can relate the key points of each overhead to the text you have read.

.Look at the section on exercises. Identify those which lend themselves to individualwork, and tackle them. Those exercises clearly constructed for teamwork, orrequiring research, may not be appropriate.

.Refer back to the narrative text as and when you need to, to complete the exercises.

.Check your answers against those given in this resource pack. Where there arediscrepancies, check through your own working to understand why the

discrepancies appeared.

8 .Use the Appendices to plan your own further development.

8A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycllng

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Il:10 United Nations Environment Programme. Industry and Environment

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Most current lead smelters separate the plastics fractions from the lead fraction during the wrecking

section. The plastic is hardly usedas a fuel any more during the smelting phase. Reagents (soda, CaO,Si02, and Fe-chips) are added in drder to reduce the lead oxide and the lead sulphates (lead paste) to

minerallead.Some smelting operations are preceded by desulphurization to reduce the generation of S02. There are

many different furnaces which can be used for the smelting process. Some of the most commonly usedare: the rotary reverberatory furnace, the blast furnace, and the stationary reverberatory furnace.


Part 3 .Technical Background Papers: Transparencies

This transparency gives a schematic presentation of a tYpical smelting section.The case-study on the lead-acid battery recycling facilitY in Part 5 ofthis traîner package also refers tothis tYpical smelting operation.

A Workbook for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling


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Remelting, alloying, and refining is carried out batch-wise in pot and kettle fumaces. Depending on thedemand, the products of refining are either liard or soft /ead. For copper removal, the temperature of the

molten lead is allowed to drop to 320.C and sulphur is added.


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operation.

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111:86 United Nations Environment Programme' Industry and Environment

Conversion ofScrap Lead intoCast Panels:

Gover slag and dust piles andclean smelting room -reducesworker exposure to lead andlead dust

$500 $9,700 3 weeks

These options were produced asjPal1 of a US AlD project, aimed at introducing cleaner productionapproaches and measures into Tu isian industries. Of course, the options presented here are flOtnecessarily feasible or possible in ail secondary lead smelters.

Cleaner production measures ar pro-active, i.e. they aim to prevent pollution rather than to clean it upat the 'end-of-the-pipe'. The cI~ er production approach, promoted by UNEP lE, is worth considering inail industries, including second lead smelters. There is a Training Resource Package available on

cleaner production from UNEP 1 .

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook fo, T,aine,sPart 3 .Techtlical Background Pa pers: Transparencies

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Part 4

Information Sources(

4.1 Introduction Iv:3

4.2 Sources of information Iv:3

4.3 Documents on lead and lead-acid batteries recycling Iv:5

4.4 Handbooks on chemicals, humans and the environment Iv:7

, 4.5 Audiovisuals Iv:8,

4.6 Some background documents on the environment Iv:l0

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8 4 Information Sources

4.1 Introduction

Part 4 contains some references to infonnation sources on lead-acid battery recycling in particular,and on recycling in general. It also contains infonnation about:

.background documents on lead-acid battery recycling,

.handbooks on chemicals, hum ans and the environment,

.audiovisuals.A reference list on general environment related issues is also included, in case the trainer requires more

8 infonnation on the most important environmental issues oftoday.

42 Sources of informationUnited Nations Environment Programme: United Nations IndustrialIndustry and Environment (UNEP lE) Development Organization (UNI DO).

UNEP lE provides a query response service, UNIDO provides an infonnation database: the

answering technical and general requests for Industrial and Technological Infonnation Bankinfonnation and documentation related to (INTIB) of UNI DO.industrial pollution. Further information:

Further information: INTIB, UNIDO, PO Box 300,UNEP lE, 39-43 Quai André Citroën, A-1400 Vienna, Austria.75739 Paris, Cedex 15, France. Tel (43 1) 21131/3705; Fax. (43 1) 2307584.Tel (33 1) 44 37 1450; Fax (33 1) 44 37 1474. Battery Councillnternational

UNEP International Register of III E Wacker Drive, Suite 600, Chicago,Potentially Toxic Chemicals (IRPTC) Il 60601, USA. Tel (1 312) 644 6610.

8 Provides infonnation on chemicals, waste EP3 (Environmental PollutiondisposaI and discharge regulations, including the Prevention Project Clearinghouse)current internationallist ofbanned or severely The EP3 Clearinghouse is an infonnation

restricted chemicals. service that collects, compiles, and assessesFurther information: technical reports, books, journal articles, and

UNEP IRPTC, Palais des Nations, other materials on pollution prevention, andCH 1211 Geneva 10, Switzerland. disseminates them to businesses and govemmentsTel (41) 22 979 91 Il; Fax (41) 22 797 34 60. in developing countries. The Clearinghouse also

UNEPIWHO/ILO International Programme provides infonnation on a broad range offor Chemical Safety (IPCS) environmental issues, and works with

Toxicological infonnation on chemicals. INFOTERRA/USA to obtain current worldwide

Further information: environmental infonnation.IPCS, cIo World Health Organization, Further information:CH 1211 Genera 27, Switzerland. EP3 Clearinghouse, 1530 Wilson Boulevard,Tel (41) 22 791 Il; Fax (41) 22791 0746. Suite 900, Arlington, VA 22209-2406, USA.

Tel (1703) 3514004; Fax (1703) 3516166.

8A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

,

1V:4 United Nations Environment Programme. Industry and Environment

}INFOTERRA 3404, US EPA, 401 M Street, "Spravochnik: ekologicheskiye ,;!

S. W. Washington, D.C. 20460, USA. organizatsii na territorii byivshevo SSSR"Tel (1202) 2605917; Fax (1202) 2603923. This handbook on ecological organisations in

Eurométaux the former Soviet Union is published by TheEuropean association representing the metal Institute for Mass Political Movements and

industries in Europe. RAU-Press. It gives contact names, the purposeFurther information: of the organizations, and ways of contacting of

Eurométaux, 6th Floor, over 800 groups and institutions.

A venue de Broqueville 12, Further information:B-1150 Brussels, Belgium. MIPP Company, 2225 Benson Avenue,Tel (32 2) 775 63 Il; Fax (32 2) 779 05 23. Brooklyn, NY 11214, USA.

European Directory of Hazardous Waste Tel (1 718) 3733173.

Management 1993/94 [1993] C. Newsome (Ed.) The International Occupational SafetyThis directory contains descriptions and and Health Information Centre (CIS)

addresses of European and Scandinavian of the International Labour Organization

companies active in hazardous waste management. Further information:Further information: CIS, International Labour Organization, ;,

Graj1am & Trotman Ltd., Sterling House, 4 route des Morillons, )66 Wilton Road, London SWI V 1 DE, CH 1211 Geneva 22, Switzerland.United Kingdom. Tel (4122) 799 67 40; Fax (4122) 7988685.

International Lead Zinc Research Organization, Inc. The Regional Environmental Center for

Further information: Central and Eastern Europe (REC)2525 Meridian Parkway, PO Box 12036, Promotes cooperation among environmentalResearch Triangle Park, N.C. 27709, USA. groups and interests in the region, acts as aTel (1 919) 361 4647; Fax (1 919) 361 1957. catalyst for developing solutions to

International Lead and Zinc Study Group environmental problems, and promotesMetro House, 58 St. James's Street, development ofa civil society. REC primarilyLondon, SWIA 1 LD, UK. supports environmental NGOs, cooperates withTel (44 71) 4999373; Fax (44 71) 4933725. local authorities, national governments, academic

MetalEurop institutions, and the private sector.

A corporation which produces lead, Further information:germanium, indium, and zinc. Active in lead, Miklos ter l, 1035 Budapest, Hungary.zinc, and polypropylene recycling. Tel (361) 250 3401; Fax (361) 2503403.

Further information: Unicorn PublicationsMetaleurop S.A., 58 rue Roger Salengro, A nonprofit environmental publishing bouse in )94126 Fontenay-sous-Bois Cedex, France. Kiev. Unicorn Publications provides readers in

Tel (33 1) 43944700; Fa.t (33 1) 43940381. Ukraine and other countries of the former SovietOECD Environment Directorate Block with books and briefings on topics related

Environmental Health and Safety Division to ecological economics, resource conservation,This division prepared a number of documents mass transportation, renewable energy, organic

on risk reduction activities for specific chemicals agriculture, etc. Unicorn translates classics ofor groups of chemicals. The first Risk Reduction western environmentalliterature into UkrainianMonograph was on lead (see background and Russian, adapting them to local conditions

documents). and culture and making them available throughFurther information: Unicorn contacts in Germany, the Netherlands,

2, rue André Pascal, UK, USA, Austria and Siovakia.

75775 Paris Cedex 16, France. Further information:Fax (33 1) 4524 1675. Andriy Glazovoy (044) 4423171;

John Spaulding (044) 2137946.

Environmental and Technologicallssues related to Lead.Acid Battery Recycling : A Workbook for Trainers ..)

Part 4 .l,ljorln(ltion Sources

r]B]; IV:S

84.3 Documents on lead and

lead-acid batteries recvcling

Advances in Recovery and Recycling: Concepts Lead Astray: the poisonous lead battery waste

and Technology Volume III [1993] trade [1994] Greenpeace

M.E. Henstock; H.R. Skov (Eds.) This publication contains basic infonnation on

Collected papers of the REC '93 International the lead tracte and recycling practices. It also

Recycling Congress, Geneva, Switzerland discusses the impact of the lead tracte in

Volume III of the collected papers contains a developing countries. The discussion is based on

paper explaining the recycling of lead. Since research done on lead recycling practices and the

more than 50% of ail recycled lead originates environmental and health impacts of lead

from used lead-acid batteries, this is an recycling in six developing countries.

interesting article which introduces the reader to Further information:

recycling schemes and the technology of lead Greenpeace, Toxic Trade Publications,

8 smelting. 1436 U St NW. Washington,

Further information: D.C. 200009, USA.

Hexagon Ltd., P.O. Box 80, Tel (1 202) 462 1177; Fax (1 202) 462 4507.

DK-IO03 Copenhagen K, Denmark. Productivity and Low Waste Technology for

Guidelines for the Management of Used Lead.Acid Reprocessing Battery Scrap [1989]

Batteries in Canada [1993] K.F. Lamm; A.E. Melin.

This publication contains a description of the ln: Productivity and Technology in the

current battery management process in Canada, Metallurgicallndustries. The Minerais, Metals

together with a set ofrecommended practices for and Materials Society.

promoting consistency in the management of Recycling Lead And Zinc:

used lead-acid batteries across Canada. The Challenge of the 1990s [1991]

Further information: Proceedings of the conference organized by the

Environment Canada, Hazardous Waste International Lead and Zinc Study Group Sub-

Division, Office of Waste Management, Committee on Recycling, held in Rome, Italy, on

Place Vincent Massey, 12th Floor, 11-13 June 1991.

351 St. Joseph Blvd., Hull, The proceedings contain papers covering the

Quebec, K14 OH3, Canada. principal aspects ofrecycling:8 Hazardous Waste: Detection, Control, Treatment .trends in world supply and demand for lead and

Part B [1988] R. Abbou (Ed.) zinc;

Proceedings of the World Conference on .the role of the secondary sectors;

Hazardous Waste, held in Budapest, Hungary, on .the extent of the recovery;

actober 25-31, 1987. .existing and developing recycling technologies;

The proceedings contain an article on a modem .environmental and health concerns and the

and low-pollutant secondary lead smelter to be regulatory framework.

set up in Hungary, and an incineration feasibility Further information:

study for battery plant trash and cru shed rubber International Lead and Zinc Study Group,

battery cases. 58 St James's Street, London SWIA lLD, UK.

Further information: Tel (4471) 4999373; Fax (44 71) 4933725.

Elsevier Science Publishers BV,

Sara Burgerhartstraat 25, P.O. Box 211,

1000 AE Amsterdam, The Netherlands.

8A Workbook for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

-

1V:6 United Nations Environment Programme. Industry and Environment

Risk Reduction Monograph No. 1: Lead

Background and national experiencewith reducing risk [1993]

This document contains infonnati~n on.the commerciallife cycle; ,

.the environmentallife cycle; 1

.links between sources and targetsl.risk reduction and control measurrs and their

cost/effectiveness;.conclusions that can be drawn regarding the

effectiveness ofrisk reduction measures, theidentification of major exposures that need tobe addressed to help risk reduction, and critical

infonnation gaps. iFurther information: 1

OECD Environment Directotate, i

Environmental Health and SafetylDivision,2, rue André Pascal, 75.775 Paris ~edex 16,

France.Fax (33 1) 45 241675.

States' Efforts to Promote

Lead.Acid Battery Recycling [1992]This report is written to help the S EPA

determine how EP A and States can most

effectively promote lead-acid batte recycling. 1tdescribes the car battery recycling hain,

characterizes State lead-acid batte recycling

requirements, and reviews the erre tiveness of

State laws in promoting lead-acid attery

recycling. .1 i

Further information:US EPA,Office ofPolicy, Planning and Evaluation,

Programme Evaluation DivisionMailcode: PM-223Z

Waters ide MaIl (WSM), 401 M Street S. W.,

Washington, D.C. 20460, USA.Tel (1 202) 2605333.

Storage Battery Technical Service Manual [1982]Published by Battery Council International.This manual gives full information on how to

handle new batteries, from transportation to

servicing.Further information:

Battery Council International, Headquarters,III East Wacker Drive Chicago, ILL 60601.

Tel (1 312)6446610.World Directory: Secondary Lead Plants [1994]

International Leadand Zinc Study Group

(ILZSG).This publication contains information on ail

smalI, medium and large sized lead smelters andrefineries operating solely or partly fromconcentrates and bullion.

Further information:ILZSG, Metro House, 58 St. James's Street,London, SWIA lLD, UK.

Tel (4471) 4999373; Fax (44 71) 4933725.


Part 4 .Information Sources11

L:;;I", 1V:7

8 4.4 Handbooks on chemicals,

humans and the environment

Chemical Hazards in the Workplace [1989] Handbook on the Toxicology of Metals

R.M. Scott. 2nd Ed [1986]

Environmental Health Criteria: Lead [1983] L. Friberg; G.F. Nordberg; V.B. Vouk.

and Lead: Environmental Aspects [1989] Health and Environmental Lead in Australia [1987]

World Health Organization, International Programme Australian Academy of Science.

on Chemicai Safety (IPCS). Occupational Medicine: Principles and Practice

Further information: [1988] Carl Zenz (Ed.)

WHO, Distribution and Sales Services, Plomb & Sante dans l'industry: Proteger les

1211 Geneva 27, Switzerland. travailleurs -Pourquoi, comment? [1990]

IARC Monographs on the Evaluation of the ln this book you will find methods to actively

8 Carcinogenic Risk of Chemicals to Humans: Some protect employees from lead exposure, the

metals and metallic compounds Volume 23 [1980] required medical surveys, and ways to recognize

World Health Organization (WHO), symptoms of lead-poisoning. The book is

International Agency for Research on Cancer. available in French.

This publication contains data on lead, Further information:

including the production processes and uses of Centre d'Information du Plomb,

different lead appliances. Péripole 118, 52 rue Roger Salengro,

Further information: 94126 Fontenay-Sous-Bois Cedex.

WHO, Distribution and Sales Services, Tel (33 1) 43944880.

1211 Geneva 27, Switzerland. Proctor and Hughs' Chemical Hazards of the

Workplace [1991]

4.4.1 Journals related to lead

Batteries International. Journal of Power Sources: The International

Quarterly published by Journal on the Science and Technology of

8 Batteries International Ltd. Electrochemical Energy Systems

Further information: Publisher:

Batteries International Ltd., Elsevier Sequoia S.A., P.O. Box 564, 1001

Aberdeen House, Headley Road, Grayshott, Lausanne, Switzerland.

Hindhead, Surrey GU26 6LA, UK.

Tel (44 428) 605536; Fa.\" (44 428) 606339.


Iv:8 United Nations Environment Programme' Industry and Environment

'"4.5 Audiovisuals )

BSB Recycling Zentrum [1989] Further information:

Video on the Blei- und Silverhütte Braubach, Ask for' Free product information No. 251'.

16 min., in German. This video explains the ChemicarEngineering,processes and technologies used in the BSB hUtte Reader Service Management, PO Box 5273,to recycle lead-acid batteries and recover their Pittsfield, MA 01203-9916, USA.constituents with the least environmental impacts. Malette PedagogiqueFurther information: This is a train-the-trainer toolkit developed by

Blei- und Silber hütte Braubach, Metaleurop (available in French). It containsBSB Recycling GmbH, 0-5423 Braubach. educational material for employees in industry on

Reduce worker exposu~e to lead how to protect themselves from lead exposure,A video and a compliance manual are available including a video, brochures, folders, posters, a

to help operators comply with US Occupational user's guide, and case-studies. It costs FF700.Safety and Health Administration lead standards. Metaleurop also organizes a two day train-the-The video explains regulatory requirements, trainer programme on how to protect personnel )

measurement options, techniques for assessing from lead exposure. The seminar costs FF3200.exposure levels and compliance methods. The Further information:manual includes detailed background Metaleurop S.A., 58 rue Roger Salengro 94,information, major requirements, 'fill in the 126 Fontenay-sous-Bois Cedex.blank' compliance forms, and a glossary of Tel (33 1) 43 944700; Fax (33 1) 43 94 03 81.

terms. Marshall Productions, Trenton, N.J,

)

..

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers ~

Part 4 .lIifornultiol/ Sources

~

Îil IV: 9

8 IChemE has an international reputation for providing high quality, effective

safety and environ mental training solutions using video, slide, open learningand computer-based techniques. We draw on experts throughout industry,the regulatory bodies, the legal profession and academia to ensure that our

training packages are bath high qua lit y and relevant.

4.5.1 Environmental packages

ENVIRONMENTAL AWARENESS ENVIRONMENTAL AUDITINGPackage EO2 Package EO4Understanding is the key to effective environmental Trainees learn how to make audits more effective. ln clearlyimprovements -bath through certified standards and effective defined sections, the package explains how to go aboutpolicy implementation. This package gives a thorough auditing a site, from defining the scope and objectives throughgrounding in environmental awareness. The case studies on-site activities to reporting and follow-up work. Thirteencover: environmentallaw; global issues; corporate issues; and case studies and exercises, supported by over 120 slides,waste minimization. include: setting up an EMS; auditing for waste disposai, dueAQUEOUS EFFLUENTS diligence and effluenœ compliance; reporting audit findings;Volume 1: awareness and treatment strategies and discussion of photographs of bad practice.8 PackageEO1 ENVIRON MENTAL MANAGEMENT SYSTEMSEngineers learn how to assess and deal with effluent Package EO5problems; senior management gain a sound technical and If you already have an environmental management system,legal grounding; and operators learn why complianœ is this package will help you gain commitment from your staff. Ifimportant. Seven case studies demonstrate how effective you are just developing a system, not only will you benefittreatment strategies save money whilst benefiting the from the training, but also benchmarking from the detailedenvironment. And the technical guidance covers: case studies will save you lime. And if you have stijl notcharacterisation of effluents; treatment strategy; safety; unit decided which system to go for (if any), this package will helpoperations; and costs. you make an informed decision.Volume 2: measurement and monitoring ENVIRONMENTAL IMPACT ASSESSMENTPackage EO13 Package EO6Trainees learn how to measure and monitor effluents, This training package gives you a thorough grounding in theensuring compliance and reducing treatment costs. ElA process and techniques. Produced in conjunction with theAIR EMISSIONS Institute of Environmental Assessment, the package providesVolume 1: key issues an effective means of training ail staff concerned with EIAs.Package EO3 There are nine case studies provided by leading environmentalThis package provides comprehensive coverage of generic air consultancies. These introduce the practical aspects of the ElApollution issues and technologies, backed up with detailed process by examining projects involving a food processing plant,sections on sourœs and types of emissions, atmospheric a sewage treatment works, a coastal defenœ scheme, a pipelinechemistry, standards and legislation (UK and European). proposai, an ail refinery and a power station.8 Volume 2: monitoring and control W ASTE MINIMIZA TIONPackage EO12 Package EO7This package follows on from AE Vol. 1: key issues, and Approaches in the package vary from good housekeeping toprovides detailed information on measurement and monitoring complex techniques such as life cycle analysis. This trainingand contrai techniques, illustrated with comprehensive case package shows how to go about il, from defining a strategystudies. Sections on ambient monitoring, meteorology and air through to making sure it happens.dispersion modelling help to provide a thorough grounding in CONTAMINA TED LANDthe technical issues associated with air emissions. Package EOBENERGY MANAGEMENT Trainees learn why contaminated land is important, how andPackage EO11 why a company should avoid contamination, and the pros andEnergy efficiency affects the bottom line. Trainees learn the cons of the key remediation techniques. You will also learnbasic tools and techniques for effective energy management. how to use this knowledge to gel the most out of the

consultants vau use

For orner form contact: Mark SmithSafety Health and Environment Department .Institution of Chemical Engineers165-189 Railway Terrace. Rugby CV21 3HQ, UK

Tel +441788 578214. Fax +441788560833


IV: 10 United Nations Environment Programme' Industry and Environment

4.6 Some background ")

documents on the environment

Saving Our Planet: challenges and hopes [1992] Beyond the Limits: global collapse or aM.K. Tolba (Executive Director of UNEP). sustainable future? [1992] D.H. Meadows;ISBN 0412473704. D.L. Meadows; J. Randers. ISBN 1 85383131 X.This book analyses the changes that have Using World 3, a computer mode l, to project

occurred in the environment in the past two the future, and by varying the basic global policydecades. It foc uses not only on the state of the assumptions, a range of possible outcomes isenvironment, but also on the interactions between described. It is shown that a sustainable society is

development activities and the environment. It technically and economically feasible, if growthhighlights the ~ain responses since 1972 to ifmaterial consumption and population are .,.,protect the envlronment. ceased down and there is an increase in the }

Published by: efficiency of our use of materials and energy.

Chapman & Hall, 2-6 Boundary Row, Published by:London SEI 8HN, UK. Earthscan Publications Ltd.,

Environmental Data Report 1993.1994 [1993] 120 Pentonville Road, London N l 9JN, UK.United Nations Environment Programme. Changing Course: a global business perspectiveISBN 0631 19043 O. on development and the environment [1992]

This report is updated biennially and provides S. Schmidheiny. ISBN 0 262 691531.

the best available data and information on a wide This book provides an analysis ofhow therange of environmental topics, including business community can adapt and contribute to

pollution, health, natural resources, population the crucial goal of sustainable development,and settlements, energy, wastes and disasters. combining the objectives of environmentalPublished by: protection and economic growth.

Blackwell Publishers, 108 Cowley Road, Published by:Oxford OX4 l JF, UK. Massachusetts Institute of Technology (MIT)

Chemical Pollution: a global overview [1992] Press, Cambridge, Massachusetts 02142, USA.

United Nations Environment Programme. Blueprint for Green Management: creating yourThis book overviews the origins and impacts of company's own environ mental action plan [1995] ..pollution around the world, caused by selected G. Winter. ISBN 0 07 709015 2. ,-

chemical pollutants and wastes. This book is a handbook of industrial ecologyPublished by: with numerous checklists for practical use and a

UNEP, Nairobi. concrete example of the Integrated System ofThe Earth Summit's Agenda for Change: a plain Environmentalist Business Management (the so-

language version of Agenda 21 and the other Rio called Winter Model), supported by the

Agreements [1993] M. Keating. ISBN 2940070008. Commission of the European Communities.

This publication is aimed at facilitating access Published by:to the very important material contained in McGraw-Hill Book Company (UK) Ltd.Agenda 21. Life Cycle Assessment: what it is and how to do it

Published by: [1996] UNEP lEThe Centre for Our Common Future, This report is in two parts. The first, Life Cycle52 rue des Paquis, 1201 Geneva, Switzerland. Assessment: what it is, is concemed with the

concept of LCA, how it is currently practised and


Pltrt 4 .Information Sources

---

1V:11

8 how it is expected to develop. lt also places LCA but systematic manner. lt illustrates the problems

in the broader perspective of other tools for involved and the kind of results that can beenvironmental analysis such as environmental produced by working through a real LCA that basimpact assessment, risk analysis and technology been used to assess the environmental impact ofassessment. different low fat spreads.

The second part of the volume, Life Cycle Further information:Assessment: how to use it, examines the several UNEP lE, Paris, France.steps involved in making an LCA in a simplified

8

8


IV: 12 United Nations Environment Programme' Industry and Environment

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Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers )

Part 4 .Information Sources

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Part 5

Training Malerial(

5.1 Introduction v:3

5.2 Some ideas for training activities v:4

5.3 Some ideas for preliminary exercises v:6

5.4 Work exercises v:8

( 5.4.1 Obstacles to a perfect recycling scheme 85.4.2 Case-study on a (ead-acid battery recyclingfacility 105.4.3 Attachments to the casestudy 215.4.4 Life cycle of lead~acid batteries and le ad 305.4.5 Comparison of lead-acid battery recycling technologies 38

5.5 Some suggestions for answers v:40

(A Workbook for Trainers : Environmental and Technologicallssues related tô'[êaCi=AêidBatterY Recycling

~--- ---

v:3

8 5 Training Malerial

5.1 Introduction

T his part contains exercises covering various issues in lead-acid battery recycling,divided into preliminary and work exercises. Preliminary exercises may be used

8 to function as homework for participants before attending a workshop or course.

The work exercises in this part require a not confronted with unexpected problems orconsiderable amount oftime and a thorough questions from the participants!study of the background readings in advance. Most exercises are based on interactive

Further notes and some model answers are processes, involving groupwork problem solving.provided to help the trainer facilitate the However, the exercises can also be doneworkshop. individually. Trainers are encouraged to adapt the

The exercises are not suitable for handing out given exercises to suit the target audiences, andas they are presented. It is left to trainers to adapt to develop additional exercises to extend the

the exercises to their particular needs. The trainer leaming experience.should first try to do the exercise, so that they are Further ideas for activities and uses of the

material in this package are given below.

8


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v:4 United Nations Environment Programme. Industry and Environment

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52 Some ide as for training ac.livities )

5.2.1 Cleaner Production

C leaner Production is the continuous explains the process of the cleaner productionapplication of an integrated preventative audit step-by-step.

strategy to processes and products, in order to Students can be asked to carry out a cleanerreduce environmental risks and impacts. The production audit at a secondary lead smelter,cleaner production approach makes use of using the above mentioned manual as amany environmental management tools, guidebook. As a result, the students couldincluding the cleaner production audit. Based identify several options to minimize wastes,on an overall mass balance of a process or site, emissions and energy use of the secondary leadidentifying raw materials, products, wastes and smelter. These options should result in moreemissions, and energy use, options are devised efficient and cost effective operations. )to minimize the generation ofwastes, emissions This assignment cou Id be a project for a team ofand energy, to improve the overall performance students, who tan spend about two months on it.of the process/site. The Audit and Reduction Sources for information on cleaner productionManual for lndustrial Emissions and Wastes, a options are available from EP3, Internationaljoint publication ofUNEP lE and UNIDO Lead and Zinc Organization, and other literature

sources mentioned in Part IV.

5.2.2 A visit to a landfili/lead-acid battery collector

M any lead-acid batteries are stored tan also be used to understand the importance ofinappropriately. This means that they recycling many other products.

either end up in ditches or uncontrolled landfills, Batteries that are dealt with properly end up at aor they go to a controlled landfill for household collector, from where they are transported to awaste. A visit may be arranged to investigate the secondary lead smelter. A visit to a lead-aciddestiny oflead-acid batteries in a landfill. Ask battery collector would give a good idea of theabout the fate of lead-acid batteries, once they practice of recycling and would enhance a basichave been dumped in the landfill. This excursion understanding of the environmental and human

threats posed by used lead-acid batteries.

5.2.3 Breaking a lead-acid battery

Consider examining a used lead-acid battery course, the acid should be removed with tare, andin class. You should be able to get one at a the wrecked battery should be disposed of

service station. Take the lead-acid battery apart appropriately after examination.

during class. While removing the differentt.t t fi th b tt 1 . th ~ t f Pay attention to, and demonstrate,

cons 1 uen s rom e a ery, exp am e la e 0.safe working procedureseach ofthem m the secondary lead smelter. Of .

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers ~

Part 5 .Training Material

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8

5.2.4 Other recyclable products

W hen considering the broader issues of If recycling schemes for certain products arelead-acid battery recycling, you may want not yet in existence, they can be developed,

to focus your attention on other products and taking the lead-acid battery recycling scheme asdiscuss in a plenary session the different an example. Ideas for products to discuss are:recycling schemes ofthese products. waste oils, batteries (dry cells), plastics, electrical

appliances, and construction material.

5.2.5 Slags

Slags from secondary Iead-smelters are ask the students to gather information on thegenerally dumped in landfills. However, national regulations on the disposaI ofsiags, and

8 when the heavy metals in the slags are other end uses of slags. Of course, the same cansufficiently immobilized, they can be used for be done for other products from lead-acid batteryother purposes, e.g. in road construction. You can recycling: ebonite, PVC, and polypropylene.

8

8 i::A Workbook for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

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5.3 Some ideas for preliminarv exercises )

5.3.1 Introduction

Before starting a leaming activity, you can Most ofthese preliminary exercises require theask trainees to prepare by giving them some trainee to collect information from a number of

preliminary exercises to do. sources. ln order to give some ideas about where toYou may also want to ask them to read some find information, a list of possible sources is given

of the articles from the background reading in below. You can give this 'checklist' to the traineesPart III before attending the leaming activity. in advance. Ask them to mark the information

sources they used for the preliminary exercise.

Newspapers University library

)International organisations Public library /

Ministries Local authorities

CD-ROM Patent office

Information hotlines Yellow Pages 1 phone book

Magazines and journals Industries

Interviews Wholesalers

Consumer organisations (International) databases

Labour unions Industrial organisations

Chambers of Commerce Non-governmental organisations )

Other: Service Sector:

5.3.2 Preliminary Exercise 1

M ake an estimate of the total number of the average life of lead-acid batteries. If data isbatteries from cars which have to be not available, estimate the number of cars by

recycled every year in your country. Go to the consulting statistical data from relevant agencieslibrary, or seek out other information sources, to (which ones?).find out the number of cars in your country and Explain your assumptions.

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers --"


~;i v:7

8 5.3.3 Preliminary Exercise 2

I nvestigate how the collection ofused lead- .Are lead-acid batteries reused in your country,

acid batteries is organized in your country. either by recharging or by cosmeticallyAlso investigate where lead-acid batteries are cleaning?collected, how and where they are stored, and .If so, how is this organised?

where they are recycled. Inquire whether it is possible to visit some.Are ail batteries recycled in your country, or are typical sites which are part of the lead-acid

they (also) exported to other countries? battery recycling network, and discuss the issues.To which countries are they sent, or from which raised in this preliminary exercise with the

countries do you receive used lead-acid batteries? manager.

5.3.4 Preliminary Exercise 3

T his preliminary exercise should be done in grid pasted with metallic lead containing variouspreparation for the exercise on the lead-acid elemental additives to increase the anode's

battery recycling facility. ln order to better hardness. The additives used depend on the battery8 understand the hazards and risks associated with manufacturer. The most commonly used additives

lead-acid battery recycling, you are asked to do a are antimony, arsenic, cadmium (although not inliterature search on the risks associated with the Europe), copper, selenium, and tin.constituents of lead-acid batteries. Table 5.1 indicates the type and proportions of

The major components of a lead-acid battery constituents of lead-acid batteries. The additivesare: and their typical concentrations ranges are given.electrodes (lead) in Table 5.2. The figures in Table 5.2 are -

.electrolyte (sulphuric acid) characteristic for Canada and USA. Cadmium is

.casing (plastic). not used as an additive in Europe, because of theThe positive electrode (the cathode) typically environmental problems which occur during

consists of a grid pasted with pure lead dioxide, recycling. Cadmium forms toxic volatiles during

and the negative electrode (the anode) consists ofa lead-acid battery smelting.

1 Search the library for information about the hazards related to each constituent.2 Which international organizations can provide information about these hazards?3 Find articles which discuss cases of lead-poisoning. Could these cases of lead poisoning in any way be

related to the activities of lead-acid battery recycling?

8

Table 5.1 Constituents of Table 52 Chemical additives to

used lead-acid batteries lead-acid batteries

Corn onent Per Cent Wei ht (typically in Canadian and US batteries)

Metallic lead 17 Additive Concentration %

Lead sul hate 50 Cadmium 0.1 -0.14

Plastic 5 Antimon 2.5 -7.5

Acid 24 Arsenic 0.15Residuals * 4 Tin 0.1 -0.5

Total 100 Co er 0.05

* The category residua/s refers to

ebonite and separators.

8 ;:::.1:A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

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v:8 United Nations Environment Programme' Industry and Environment

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5A Work exercises )

5.4.1 Obstacles ta a perfect recycling scheme

l n many countries, the recycling rate oflead- exercise. You will find this article in theacid batteries is around 90 per cent. However, background reading in Part /II.

despite the fact that recycling networks are weIl The article suggests that the lead-acid batteryorganized in many countries, recycling rates are recycling network typically consists of four

unlikely to reach 100 per cent. elements: the consumer, the transportation

ln this exercise, you will identify why a network, the battery breakers, and the smeltinghundred per cent recycling rate cannot be operation.achieved, and why and where in the lead-acid The relationship between these categories is

battery recycling network environmental and shawn in the first figure in the article. Note thathealth risks arise. this network is only part of a bigger network for

The exercise can be done individually as weil lead-acid batteries in general. This biggeras in a group. ldeas for answers are provided by network consists of: '1the trainer. Other appropriate solutionsmay also .battery manufacturers !

be identified during a plenary session. .consumers (car producers/sellers/buyers)Read the article on Current Management .lead-acid battery collectors (storage)

Practices for Used Lead-Acid Batteries in andCanada before answering the questions in this .secondary lead-smelters (see Figure 5.1).

Figure 5.1 The battery life cycle (Metaleurop, France)

P fT rt @1J~cProofTransportroo ranspo

D./ "" Polypropylene~~ hortiCUlture ..' / .automobile parts

~ Proof Storage Secondary'::::~ Smelter

User" / Acid treated,

recovered or-ii,~, neutraiizedBattery Producers

Aillead-acid batteries have to be collected and country in the world. ln some countries, arecycled in order to minimize the environmental recycling rate of more than 100% bas beenand healthrisks of inappropriate disposai. Also, achieved, but this is a result of a delay in batteryaIl environmental and health risks should be collection in the previous year.

minimized during the collection of lead-acid ln the following exercise, you are asked to clarifybatteries, and storage of used lead-acid batteries why a yearly recycling percentage for lead-acidshould be avoided as much as possible. As is batteries of 100% bas not been achieved in anyclear from the background reading in Part /II, country, and what environmental and health risksthis ideal situation has not been realized by any arise in the lead-acid battery recycling network.

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers '"


1: v:9

8 ê1t'j;j;~ 1 (a) What constrai~ts are there to prevent the consumer {rom delivering a lead-a

'êêêêê 1 ~ battery to the retaller, collector, or drop-off depot?

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1 1êê"\êiê'~CC

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(h) What environmental threats and health risks occur when the consumer keepsthe batteries "in-house" for a long time?

1 1

Some suggestions for answers to this question are on page v:40

8 2 (a) Considering the transportation network, what constraints prevent delivery ofthe batteries to the battery breaker or the secondary lead-smelter?

1 1

(h) What environmental threats and health risks occur when the batteries are storedcommercially for a long time?

1 1


3 (a) Considering the battery breaker, what constraints are there to prevent deliveryof the batteries to the secondary lead-smelter?

8 1 1

(h) What environmental threats and health risks occur when the battery breakerkeeps the batteries for a long time?

1 1


8A Warkbaak for Trainers : Environmental and Technologicallssues related to Leâd:AcidBâtt~~Recycling

v:lO United Nations Environment Programme' Industry and Environment

5.4.2 Case-study on a lead-acid battery recycling facility )

T his exercise is based on a case-study describing the recycling process of lead-acidbatteries at a recycling facility, and is best clone after Preliminary Exercise 3.

The participants will -either individually or in a group -do some exercises, which insome cases require a technical background.

The infonnation needed to answer some of the with the case-study before asking the participantsquestions in this exercise is provided in the to do the exercises.attachments at the end of the exercise. The case-study is based on the article 'A

The results may be discussed in a plenary modern and low-pollutant secondary lead smeltersession, and ideas for answers are again provided to be set up in Hungary' included in theat the end of this Part. The traîner should work proceedings of the World Conference onthrough the exercises tirst to become comfortable Hazardous Waste: Detection, Control, Treatment

(See References in Part [J').

Introduction )

T bis exercise concems a medium sized remaining equipment, and emissions increasedsecondary lead-smelter with an annual dramatically. Dust conditions within the plant

capacity of 25 000 tonnes, located near a became intolerable, and during the last week ofrecreation area. The plant processes used lead- 1979, a decision was made to effectively bypassacid batteries and lead scrap. Only the smelting the main pollution contrai facility and continueand recycling of the used lead-acid batteries are operations.considered for the purpose of this exercise. The bypass continued until April 1980 wh en

Secondary lead smelting is a highly polluting repairs were tinally completed. Several childrenprocess, and has been related to many health were hospitalized, and extensive blood samplingproblems in the past and in the present. The revealed that 95% of ail children in the vicinitysecondary lead smelter described in this exercise had blood lead levels in excess ofO.2mg/1 (EECwas responsible for serious environmental limit, 1977). As a consequence, many residentsproblems in the late 1970s. An unfortunate were relocated, and homes nearest the smeltercombination of events culminated in extreme were purchased and destroyed. Several emissionemission rates that poisoned most of the young contrai projects were undertaken. Streets werechildren playing in the vicinity. The tirst ofthese cleaned and dust producing areas were watered. 9events was related to a change in ownership in Home gardening was discouraged. Clean topsoil,1977 that introduced a new management sand gravel, grass seedings and water subsidiesphilosophy to the facility. Smelting capacity was were provided to promote the general rec'overy ofincreased by about 35%, and the smelter the community.operators elected to install new production Needless to say, these corrective actions wereequipment before upgrading pollution contrai. very costly. Additionally, the secondary lead

ln the late 1970s, during a period of smelter developed a bad public image. Sinceextraordinarily high lead prices, an attempt was these accidents, the plant has been committed tomade to improve air pollution control while the meeting stringent environmental restrictions,smelter operations continued at the maximum especially with respect to the following focalcontraI capacity. The result was a tire that points:disabled approximately 60% of the smelter's .complying with the strict regulations on leadparticulate air pollution control capability. emission;However, operations continued with the .providing for optimally clean workplaces.

Environmental and Technological Issues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers --'

Part 5 .Training Mater;a/

ffl~: ,61ig"ïiliBil v: Il

8 Process description

The processes in the plant involve the which is then conveyed to the acid tank for

following three operations: further use. The refmed lead is stored outside to1 Wrecking the batteries. cool down, after which it is transported to lead

2 Smelting the prepared batteries and lead manufacturers on Tuesdays and Fridays.slurries by the oxygen process in a short rotary Table 5.3 indicates the type and proportions offumace. constituents of lead-acid batteries, based

3 Refining the bullion discharged from the short primarily on the lead-acid automotive battery.rotary fumace and the scrap lead kettles.The layout of the plant described above T bl 53C t' t t f.

h fi Il .. ( F . 5 3 a e. ans 1 uen s acomprIses t e 0 owmg sections see 19ure . d 1 d 'd b '

in the attachments). use ea -aGi atterles

.wrecking section with storage areas for battery Corn onent Per Cent Wei htscrap and lead slurries; Metallic le ad 17

.storage bins for fluxes and recycling products Lead sul hate 50

8 and ~eighing. unit for these materials; Plastic 5

.smel~mg sec~lon; Acid 24

.refinmg section;..Residuals * 4

.filtenng section.The batteries collected from scrap yards, Total 100

wholesalers, and service stations are brought tothe facility on Tuesdays. The batteries are stored * The category residua/s refers to ebonite and

in an outdoor stockyard from where they are separators.transported to the wrecking section's loader bybulldozer. The stockyard, loader, and crusher aredrained during the wrecking phase to collect acid

Wrecking of the battery scrap

A mOdern and relatively simple process bas drainage of the acid. The acid is separated on abeen chosen for battery wrecking, vibrating screen, and discharged into a settling

involving a minimum of machinery. The process tank where entrained slurry is allowed tobas been exactly tailored to the specified capacity deposit. It is finally stored in a tank for further

8 of 1.0 million batteries/year. use. ln this phase, 95% of aIl acid is separated

The process eliminates operations which -from the batteries.based on modem findings -are superfluous, such .shredding of the batteries and separation ofas the removal of grid metal and oxide or the polypropylene (and of light plasticsremoval of separators. The quantity of acid respectively): the batteries, freed of liquid acid,removed by the ventilation system is less than 1 % reach rotary shears. They are cut up and thenof the total acid content of the batteries, and dropped into a neutralization tank, together withtherefore negligible for the calculation of the the lead paste. The paste is a mixture of leadmass-balance. However, in order to meet the oxide and lead sulphates. The solids aremost stringent health and safety standards, the discharged from the neutralization tank byventilation system is crucial. means of a screw, and then passed on to

The process involves the following operations: intermediate storage. If desired, the floating.removal of sulphuric acid: the batteries reach a polypropylene may be discharged separately at

spike crusher via a vibrating feeder and a chain this point. The lead paste is collected in the

conveyor. They are perforated to enable


.._,- ,.", --" ..,. ..,..,

V:12 United Nations Environment Programme. Industry and Environment

thickener from where it is discharged to storage and completely bumed with the heavy plastics, )for lead fraction. thus utilizing the caloritic value of the latter.

.neutralization oft/le adhering residual Impacts on the environment resulting fromsulphuric acid is carried out in the neutralizing plant operation are avoided by the followingplant, to avoid volatilization of SO3 inside the measures:fumace. The liquid contained in the tank is .the chain conveyor for battery transportation istransferred by pumping, and neutralized with sprinkled with water to avoid dust generation;hydrated lime. The solids content is kept .both the spike crusher and the rotary shears areconstant by separation of a slurry portion. On operated at low speed (less than 100 rpm) (0average, the ratio of Ca(OH)2 to sulphuric acid counteract the formation of dust and of aerosols;is 1.2: 1 on a weight basis. .accumulating splash water is recycled, whichThe polypropylene product is put into the means that no waste water is generated;

fumace together with the lead-bearing fraction, .plastics with residuallead content are Dot

dumped.

Now answer the following questions:

4 (a) Give three reasons why the sulphuric acid is separated from the lead containing ")

fraction:

(b) What is the main environmental problem related to SO3 and SO2 in theatmosphere?

(c) ln some secondary lead smelters, the lead sulphate in the paste is desulphurizedwith Na2CO3. Give the reaction equation, and explain why the lead paste isdesulphurized before the smelting process:

Some suggestions for answers to this question are on page V: 40

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaok for Trainers ~


~dl v:13

8 CM 5 Refer 10 Table 5.3. ln this exercise you are asked to calculate a mass balance for

1 the wrecking process for ail components of the lead-acid battery.

'yI Assuming an average weight of the lead-acid batteries of 17 .2kg, calculate how",! 'many kg ofmetallic lead, lead sulphate/oxide, plastics and residuals per used lead-acid battery are collected at the end of the wrecking operations.

"Residuals" refers to ebonite and separators (90%), and iron (10%).

8 The answer to this question is on page v:40

l n secondary lead smelters in developing in a container at arrivai, and from therearecountries, it bas often been the case that the transported to a place where the actual breaking

batteries are broken manually, without proper of the batteries takes place. The acid is allowed toprotection for workers. This is to allow release of fUn off to a settling tank through a gutter, wheresulphuric acid before smelting (Greenpeace it is neutralized before being released into a local

report Lead Astray: the poisonous /ead battery waterway. The plastic battery cases are cleanedwaste trade [1994 D. by band in rinsing baths at the workplace and

For the next question, assume that -in then stored in a container, which serves as a

developing countries -the batteries are dumped collector for the feed to the smelter.

6 (a) What dangers are the workers exposed to during the battery wreckingoperations in developing countries? (See a/so background materia/ and Materia/sSafety Data Sheets):

8

(b) What protective provisions would be necessary to prevent exposure to thesehazardous substances? (See a/so background materia/ and Materia/s Safety Data

Sheets):

Some suggestions for answers to this question are on page V: 40



Smelting the correspondingly prepared batteries and lead

slurries by the oxygen process in a short rotary furnace

T he prepared batteries, a.long with recycling in this particu!ar ca~e enables the smelting of

products from lead retimng (drosses), flue battery scrap mcludmg the complete plasticdusts, and reagents (soda, CaO, SiO2, and Fe- material. This plastic portion is bumed smoke-chips), are smelted with oxygen in two short free with full utilization of its heat content. Torotary fumaces. During smelting, the antimony, achieve this, the crushed batteries are charged

arsenic, tin, calcium, aluminium, and other into the fumace with the aid of a vibrating feederalloying elements in the grids are oxidized to the (see Figure 5.5 in the attachments) more slowlyslag, while lead is reduced and recovered as a low than usual. During this feeding operation, the

impurity bullion. fumace revolves slowly, either continuously orThe dust and recycling products from the lead intermittently, with the bumer ignited.

retinery make up 10% of the total weight of the During combustion of plastics, the fuel oïl feedinput into the rotary oven, and the reagents added rate is decreased, but the oxygen feed rate isto the smelter make up a further 5%. increased.

The smelting section consists of a feeding Such retarded feeding and immediate ignitiondevice and two short rotary fumaces with 3.5m and combustion of the plastic material avoids Dot

diameter, equipped with oxy-fuel bu mers of only an uncontrolled, sudden evaporation of thespecial design with a capacity of 30-300kg of volatiles contained in the plastic material, butfuel oil/h and 50-600Nm302/h. also incomplete combustion. These phenomena

The essential features ofsmelting with oxy-fuel can hardly be prevented if the fumace, fullybumers are: charged with plastic-containing batteries, is

.reducedfuel ail consumption, i.e. from ignited and tumed.

approximately 90kg/t of scrap to approximately The ratio between material and oxygen feed40kg/t ofscrap; rate and, consequently, the plastics combustion

.shortened chargillg period and, consequently, capacity of the fumace, cao be controlled in suchincrease in capacity; a manner that the plastics are bumed unhindered

.reduced generation of dust and therefore, an and smoke-free. As soon as charging of theincreased direct metal recovery (maximum dust fumace and combustion of the plastics havecontent in the cleaned waste gas is 2.5mg/Nm3); tinished, the fuel oïl feed rate is increased and the

.and (an important advantage for environmental batch is processed.

protection) reduction in waste Kas volume from ln the short rotary fumace, both oxidizing andapproximately 12m3/kg of fuel oïl when using reducing conditions are produced simultaneously.air for combustion to approximately 3.2m3/kg The antimony, arsenic, tin, calcium, aluminium,of fuel oïl when using oxygen. This reduction and other alloying elements in the grids andofwaste air, in combination with a lower lead straps is oxidized to the slag while lead iscontent of the flue dusts (from 50% to 35%), reduced and recovered as a low impurity bullion.minimises lead emission. The slag composition is shawn in Table 5.4.

The temperature of the waste air is about 1200°Cwhen leaving the fumace, and it has:o be rap~dly Table 5.4 Slag composition in per cent weight

cooled down to below 300°C to avold formatIon ofdioxins. Dust from the waste air handling system is PbO 20. 30

caught in a combination of electric precipitators, Sb203 4. 8

bag filters and scrubbers. The dust is then SnO2 0.5 .2discharged into the short rotary fumace. AS2O3 0.5 .1

Until now, the use of oxygen in a short rotary CaO 4. 10fumace was limited to the smelting of metal and SiO2 7 .17

lead paste after removal of the plasticcomponents. The modem oxygen process applied

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers ./


r:; v:15

8 For meeting the requirements on clean number of ladIes needed for one lead and/or slag

workplaces, it was stipulated from the beginning tapping operation. The ladIes are kept under the

of the project that feeding and tapping are carried hood with the suction system permanently

out with the suction system continuously operating until the melt surface has solidified and

operating. For that reason, both ends of the short smokeless transportation is possible. The charge

rotary fumaces have been equipped with hoods. is taken to a vibrating feeder with the aid of an

These hoods (at both the tapping and the feeding enclosed chain conveyor. The feeder bas also

end) have been designed in such a manner that been integrated in the hood, thus completely

they offer enough space to accommodate the avoiding dust formation during fumace feeding.

Now answer the following questions.

7 Due to the use of oxy-fuel bumers, the generation of lead in dust bas decreased

considerably. Exactly how much has lead in dust been reduced, per tonne of

battery scrap?

8

The answer to this question is on page v:4/

8 Calculate the fractions of the constituents and the total weight of each load in the

two short rotary fumaces, based on an annual capacity of the facility of 1 million

used lead-acid batteries. Assume the fumaces are in operation for five days a week,

42 weeks a year. The fumaces are charged five times per day:

8

The answer to this question is on page v:4/

8A Workbook for Trainers : Environmental and Technologicallssues related to Lead.Acld BatteryRecycling

""


"Due to new environmental regulations which will be enforced in the near future, the recycling plant will ê)

have to separate ail components of the batteries. Therefore, the wrecking process has to be changed.

,0

9 Design the new processflow-diagram of the wrecking process.l, Make a process-flow diagram, using boxes to illustrate the separation process,~il and arrows to indicate the direction of the flow of the materials. Separation\fW techniques based on size distribution and hydrodynarnic characteristics will suffice

for separating aIl end products. The end products are: grids, lead paste,PVC/ebonite, acid, and polypropylene. Use water for the different separationphases and neutralization phases:

A suggested answer to this question is on page v:4!

10 Due to the separation phase, polypropylene and acid can be processed and sold asraw materials.

(a) Do you expect that the capacity of the smelters will change due to the newseparation process?

(h) How will the energy consumption per tonne of lead change?

Answers to this question are on page v:41

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers


...

1 v:17

8 Refining of bullion discharged from the furnace and of scrap lead

R: fining ofbullion is carried out by a intennediate product being handled andtandard process (kettle refining) in five transported uncovered.

kettles of 50t capacity each. Refming will include The hoods (see Figure 5.6 in the attachments)the following operations: have been designed in such a way that the.smelting and drossing; elements (i.e. an agitator, a pump, or an agitator.coppeT removal; joined to a withdrawing unit) can be integrated.softening (antimony removal); into the hood. The quantity ofsucked-offwaste.final clean-up, alloying and casting. air is automatically adjusted to the minimum

Lead refining is known to have environmental volume required for each operation, thugimpacts and to be hazardous to the health of minirnizing the overall quantity of waste airworkers. The removal of reaction and discharged from the refining plant.intennediate products from the kettle is The drosses are removed with the aid of a screwparticularly dangerous because it often involves conveyor. Previously, the drosses were removedsignificant danger for the personnel due to the manually, causing a serious deterioration inoccurrence of lead-bearing dusts and high working conditions. The screw conveyor can be

8 temperatures. vertically adjusted for varying the immersionTo eliminate these dangers and for meeting the depth into the fluid layer. The fluid layer is

requirements of national labour regulations, the moved by an agitator towards the inlet opening offollowing technical appliances are provided: the screw conveyor, lifted beyond the kettle rim.hoods for the kettles enabling an automatic by the spiral grooves of the screw, and

adjustment of the waste-air volume; continuously transferred into a closed container..mechanical removal of drosses and transfer of After dross removal is complete, the container

these into closed containers; content is allowed to cool down. The cooled.pneumatic transportation of the drosses from content is sucked off with a suitable device and

the containers into the bins; pneumatically delivered into a bill..transportation of the drosses from the bills to The method explained above pennits removal

the short rotary fumace in enclosed conveying of the fluid reaction products from the meltunits. surface and transportation to the biG sectionThe above description shows that aIl process without involving any danger for the operating

operations, including transportation, are staff.perfonned in closed containers without any

8 Conclusions

T he plant described above has been designed Two end products are discharged from theto produce approximately 60% of quality plant: market lead and slag, originating from the

99.95% purity and the balance of approximately short rotary fumace which is taken to a dump.40% of hard lead, based on the intended annual This slag is the only loss and waste productquantity of feed material of one million lead-acid accumulating in the plant.batteries. An overall recovery of 97.2% will be Apart from the measures described above,obtained. Any intennediate product accumulating several other technical and organizational actionsin the plant, such as flue dusts and drosses, are have been implemented for ensuring as clean arecycled. This is also true of service- and process workplace as possible. The most important ofwater. Chlorine, ifany, originating from PVC is these additional measures are:precipitated with lead flue dust and transfonned .Ali walls and ceilings of any plant section areinto a rotary fumace slag in special flue dust smooth on the inside;

campaigns.

8A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Rêêycllng

"""-- "." ",","L~'""""~-


.Sprinkling systems for walls are installed to accessible via gales. and are supplied with air )

permit cyclic washing; from outside over high-duty tilters..Floors and platforms are inclined towards the Processing ofbattery scrap and lead residues is

drain and the channel: water spray nozzles are certainly a difficult problem to tope with becauseinstalled at elevated points for cyclic sprinkling oftoxicity of the lead and complicated handlingof the surfaces; operations. The plant design described above

.Essential plant areas have been laid out in such shows that the application of moderna manner that no vehicles are required, thus technologies and improved working conditions toeliminating the entrainment of dust deposits; standard technologies permit the erection of a

.Contrai stands and short-break rooms, as they plant at reasonable expenditure which meetsare called. have been built: these are only current job and environmental regulations.

Now answer the following questions.

Il (a) What environmental threats does the secondary lead smelter pose to ilsvicinity? Discuss, for each stage of the process, the operations and substanceswhich may cause environmental pollution during normal operations: )

(h) What about when there is a malfunction/accident in the facility (e.g. tire,collision, open valves, etc.)?

1 1

Suggested answers to this question are on page v:41

12 (a) For what purposes could the slags be used, instead ofbeing dumped at a.,.

landtill7 )0,{

(h) What environmental problems can slags cause when used for these purposes,taking into account the origin and contents of the slags?

1 1

Suggested answers to this question are on page v:42

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers .)

Part 5. Training Material

i v:19

8 13 During the smelting and refining process and the recycling of dust, a lot of energy

is used and wasted as heat. Where in the total process could you reuse the heat lostduring smelting, refining and cooling, in order to save energy during the smeltingand refining process?

8Ideas for answering this question are on page v:42

14 According to the World Bank report on Occupationa/ Hea/th and SafetyGuide/mes, exposure to employees should never exceed 5Omg/m3. The plantdescribed above fulfils these norms, thanks to the hood structure above thefumaces. Before the hood structure was installed, a ventilation system removed thelead particles from the hall.

Assume that the hall where the two short rotary fumaces are located has a volumeof3600m3. When in operation, the two short rotary fumaces together emit 60g/h oflead in particle form per 1m3, due to leaks. How many cubic metres must theventilation system be able to clear of lead per hour in order to keep the leadparticle concentration below the limit?

8

A suggested answer to this question is on page v:42

8A Workbook for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery

,"c."""'"- -.""_.~..,',,.."..~"~ c."'""."


"" 15 Fugitive emissions arise during various batch and transfer operations. ln addition, )

iî. waste treatment procedures also play a significant raIe. Accordingly, emissions{î.~ from a process can vary considerably, depending on the degree of'goodfl;\j housekeeping practice', supervision and contraI exercised at a plant.

Give suggestions on how to reduce human exposure to lead through 'good

housekeeping practices':

Suggestions for answers to this question are on page v:43

16 How should the design of the batteries be changed in order to reduce theenvironmental impacts during the recycling process? Keep in mind that theperformance of the battery must not be reduced:


17 8ased on the lead recuperation rate at the refinery, how many batteries can beproduced only using lead which is produced by this secondary lead smelter?Assume that new batteries contain IOkg of lead.


Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers ./


ï[.i~ v:21

8 5.4.3 Attachments to the case study

Figure 5.2 Model for air emission inventories and controls

PROCESS UNIT T5P 502 Nax 1 co VOC(UI kQ/U kg/V kgjU kgjU kg/V kg/V

Fabric filter tn of Pb 0.07SECONDARY LEAD PROCESSINGPretreatment

Sweatina furnaœFuqitive emissions tn of Pb 1.3 Pb 0.55Uncontrolled tn of Pb 25.5 Pb 6Control/ed tn of Pb 0.25 Pb 0.06

SmeltingFuaitive emissions tn of Pb 8.2 Pb 2.19

Reverberatory FurnaceUncontrol/ed tn of Pb 162 40 Pb 32

8 Control/ed tn of Pb 0.5 40 Pb 0.1Blast (cu pola)

Uncontrol/ed tn of Pb 153 27 Pb 52Control/ed tn of Pb 1.12 27 Pb 0.15

RefininaKettle refinino

Uncontrol/ed tn of Pb 0.02 Pb 0.006Control/ed tn of Pb

Kettle oxidationFabric filter tn of PbO >20.0 PbO >20.0

STORAGE BATTERY PRODUCTIONUncontrol/ed * 11000 batteries 63.2 1 Pb 6.94

Control/ed 1000 batteries 3.2 Pb 0.5PRIMARY ZINC 5MEL TING Pyrometaliuroicai process

Fuaitive emissions tn of zinc 3.85Roasting

Multiple hearth roasterUncontrol/ed tnofzinc 113 1100Cyclone + ESP tn of zinc 0.5 1100

8 H1SO4 oient tn of zinc 0.34 33Suspension roaster

Uncontrol/ed tn of zinc 1000 1100Cyclone + ESP tn of zinc 4 1100

H1SO4 oient tn of zinc 3 33Fluidized bed roaster

Uncontrol/ed tnofzinc 1083 1100Cyclone + ESP tn of zinc 4 1100HzSO4 plant tn of zinc 3.2 33

Sinter olantUncontrol/ed tn of zinc 62.5 110Cyclone tn of zinc 24.1 110Cyclone + ESP tn of zinc 8.25 110

* A fabric filter is considered an integral part of the lead oxide mill, ifany.


" ""'~.".,'""."'."...


Figure 5.3 Overall plant layout

--~ ~- =*=~.oDt-;;;;;;:

r --

'--j

Battery Wrecking :

Storage i

Source: A Casting StorageKHD

HUMBOLDT .WEDAO Smelting Reflning

Figure 5.4 Wrecking section

,---, 11 1 1 111 l' 11 1 1 l

, ~~ II 1 1 1 1 1.a ' 1

.1 . ~ " 1 Spikecrusher""p l'~ ( ~ 1 1 2 Acldseparator

, -~. ~~~: : 1 3 Rotary shear

: ::: 4 Neutralisation tank and1 1 1 1 ~ polypropyiene discharge1 1 1 l ' ,1 1 " 1 5 Thickener

L Y '1 : 6 StorageforieadfractJon, - , 1 11 1 1 11 1 1l '1 1

11 1 1 1--' --1-'1 "' 1 11 1 1 1 1 11 1 ~ --. 4 1 1 1 III 1 1 1 III 1 1

1 1 1 : 1_-~r 1 :1 IL:-.J 1 -11 Ip- 1 ' 11 1 1 11 1 1 1 11 1 1 1l' : 1 11 1 PI' 11 1 ~ l , Y1 L___' L T 1l '-@-! L 1

: @@ : A1 L _1 1 Source: ~1 1 1

K1 1 HO1 1 HUMBOLDT

~ ~ WEDAO


Part 5 .Training Materia/

.a~ ~";;**}~~I""&i'M":471'7:\'I1!fif~r,''''l'''~i~.i.i Dlnln e atenal' v.23',",iYi"4",h~c,"" 'c'"O:"","\':ccc"'"","" .

8Figure 5.5 Short rotary furnace with hood

sourcA8 KHDHUMBDLDT

-WEDAG

Figure 5.6 Kettle with hood, agitator and removing screw

source:! .,KHD 1

HUMBOLDT l'_WEDAG "

"

;

\

8


"",,. ". , "°".""".,


')"Figure 5.7 Material Safety Data Sheet for lead (inorganic)

Lead (inorganic) ICgC: 0052

CAS# 7439.92.1 Lead metalRTECS# OF7525000 PlumbumICSC# 0052 Pb

Atomic mass: 207.2

Types of Acute Prevention First aid/Fire fightingHazard/Exposure Hazards/Symptoms

FIRE Not combustible

EXPLOSION

EXPOSURE Prevent dispersion of dust!Strict hygiene!

.Inhalation Headache, nausea, Local exhaust or breathing Fresh air, rest, and refer forabdominal spasm. protection medical attention

.Skin

.Eyes

.Ingestion Headache, nausea, Do not eat, drink, or smoke Rinse mouth , induce vomitingsore throat, during work. (only in consc;ous persans/)abdominal spasm. and refer for medical attention

Spillage Disposai Storage Packaging and Labelling

Sweep spilled substance intocontainers, carefully collectremainder (extra personalprotection P2 filter respirator forharmful particles).

Additionallnformation )

l SEE IMPORTANT INFORMATION ON BACK 1

ICSC: 0052 V1.0 Prepared in the context of cooperation between theIMPORT ANT LEGAL NOTICE ON BACK IPCS and the Commission of the European

Communities @ CEC, IPCS, 1990

continued ...

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers /


"- ..."~.'c-

li9Tiifillï v:25

8Important data Physical State Appearance: Inhalation Risk:

Bluish white or silvery grey solid in various Evaporation at 20'C is negligible: aforms. harmful concentration of airborne parti ci esChemical Dangers: Gan, however, be reached quickly.

The substance decomposes on heating, Effects of Long- Term or Repeatedproducing toxic fumes. The substance is a Exposure:strong reducing agent. The substance may have effects on theOccupational Exposure Limits: nervous system and kidneys. .This

substance may cause anaemla and cold.TLV ppm 0.1Smg/m3 (as TWA) (ACGIH May impair male fertility. May cause1989). PDK (as aerosol) 0.007mg/m3 retarded development of the new-born.0.01 mg/m3 C (USSR 1988). Danger of cumulative effects. Effects may

Routes of Exposure: be delayed.

The substance Gan be absorbed into thebody by inhalation and by ingestion.

Physical Boiling point 1740'C8 properties Melting point 327'C

Relative density (water = 1) 11.3

Solubility in water ,.. noneVapour pressure, Pa at 2S'C < 0.1

Environmental This substance may be hazardous to the environment. Special attention should bedata given to air pollution. ln the food chain important to humans, bioaccumulation takes -

place specifically in shellfish.

Notes Explosive limits are unknown in literature. Depending on the degree of exposureperiodic medical examination is indicated. Do NaT take working clothes home.

Refer also to Cards for specific le ad compounds e.g. Lead chromate (ICSC # 0003),Lead (II) Oxide (ICSC # 0288).

Additionalinformation

8

1 ICSC: 00S2 @ CEC, IPCS, 1990 Lead (inorganic)

1 LEGAL NOTICE Neither the CEC nor the IPCS nor any person acting on behalf of the CEG or the IPCS isresponsible for the use which might be made of this information.


"~."'"'..


"

Figure 5.8 Material Safety Data Sheet for lead (II) oxide

Lead (II) Oxide ICgC: 0288

CAS# 1317-36.8 Lead monoxide HAZARD SYMBOLICSC# 0288 PbO Consult nationallegislationEC# 082-001-00-6 Molecular mass: 223.2

Types of Acute Prevention First aid/Fire fightingHazard/Exposure Hazards/Symptoms

FIRE Not combustible ln case of tire in thesurroundings, ail extinguishingagents allowed.

EXPLOSION

EXPOSURE Prevent dispersion of dust. Strict hygiene. Avoid exposure ofpregnant women. Avoid exposure of adolescents and children

.Inhalation Cough, headache, Local exhaust or breathing Fresh air, rest, and refer fornausea. protection medical attention

.Skin Redness. Protective gloves. Remove contaminated clothes,rinse skin with plenty of wateror shower.

.Eyes Redness, pain. Safety goggles. First rinse with plenty of waterfor several minutes (removecontact lenses if easilypossible) then take to a doctor.

.Ingestion Abdominal cramps, Do not eat, drink, or smoke Rinse mouth , give nothing toconstipation, diarrhoea, during work. drink, and refer for medicalheadache, nausea, attentionvomiting.


Sweep spilled substance into Separated from sodium, Further information on labelling:containers, carefully collect aluminium. Consult nationallegislation.remainder (extra personalprotection P2 filter respirator forharrnful particles).

L. Additionallnformation 1

1 SEE IMPORTANT INFORMATION ON BACK 1

ICSC: 0288 V1.0 Prepared in the context of cooperation between theIMPORT ANT LEGAL NOTICE ON BACK IPCS and the Commission of the European

Communities @ CEC, IPCS, 1991

continued ...



fIli': v:27


Red to yellow-red crystals. Evaporation at 20'C is negligible: aChemical Dangers: harmful concentration of airborne particles

can, however, be reached quickly ifThe su~stanc~ decomposes on heating, powdered.produclng tOXIC fumes (see ICSC#0052).Reacts violently with sodium and Effects of Long- T erm or Repeatedaluminium. Exposure:

Occupational Exposure Limits: The substance may have effects on3 haemosynthesis, resulting in anaemia.

TLV (as Pb) 0.15mg/m (as TWA) (ACGIH Disturbance of the central and peripheral

1988-1989). nervous system and damage to theRoutes of Exposure: kidneys may occur. May impair maleThe substance can be absorbed into the fertility. This compound may disturb thebody by inhalation and by ingestion. development of the central nervous

system of the newborn.

Physical Melting point , 888'Cproperties RI' d . ( _ 1)8 e atlve enslty water 9.5

Solubility in water """""""""'" none

Environmentaldata

Notes Aiso consult ICSC #0052 on lead (inorganic).

Additionalinformation

8

ICSC: 0288 @ CEC, IPCS, 1991 Lead (II) oxide 1

LEGAL NOTICE Neither the CEG nor the IPCS nor any persan acting on behalf of the CEG or the IPCS isresponsible for the use which might be made of this information.

This card contains the collective views of the IPCS Peer Review Committee and may not reflect in ail cases ailthe detailed requirements included in nationallegislation on the subject.

The user should verity compliance of the cards with the relevant legislation in the country of use.

8 :A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

~ """'" ""'"",..,


Figure 5.9 Material Safety Data Sheet for sulphuric acid

Sulphuric Acid ICSC: 0362

CAS# 7664.93.9 Sulphuric acid HAZARD SYMBOLRTECS# WS5600000 H2SO4 Consult nationallegislationICSC# 0288 Molecular mass: 98.1UN# 1830EC# 082.001.00.6

Types of Acute Prevention First aïd/Fife fightingHazard/Exposure Hazards/SymptomsFI RE Not combustible. Many No contact with flammable No water.

reactions may cause substances.tire or explosion.

EXPLOSION ln cases of tire, keep drums etc.cool by spraying with water but nodirect contact with water.

EXPOSURE .Avoid ail contact!

.Inhalation Sore throat, cough, Ventilation, local exhaust, or Fresh air, rest, half-uprightlaboured breathing. breathing protection. position, artificial respiration if

indicated, and refer for medicalattention.

.Skin Pain, serious skin Protective gloves, protective Remove contaminated clothes,burns. clothing. rinse skin with plenty of water

or shower, and refer for medicalattention.

.Eyes Pain, severe deep Face shield or eye protection in First rinse with plenty of waterburns. combination with breathing for several minutes (remove

protection. contact lenses if easilypossible) then take to a doctor.

.Ingestion Severe pain, vomiting, Do not eat, drink, or smoke Rins~ mouth , gi.ve plenty of. ~atershock. during work. to dnnk, do not Induce vomltlng,

and refer for medical attention


Evacuate danger area, collect leaking Separated from other materials Unbrea~ab~e packing: put breakableliquid in seaiable containers (extra (see Notes), store in stainless steel pack~gmg Into clos~d unbre~kablepersonal protection: complete containers. container. Further Information onprotective clothing including self- labelling: Consult national /egislation.contained breathing apparatus).

1 Additionallnformation 1

1 SEE IMPORTANT INFORMATION ON BACK 1

ICSC: 0362 V1.0 Prepared in the context of cooperation between theIMPORTANT LEGAL NOTICE ON BACK IPCS and the Commission of the European

Communities @ CEG, IPCS, 1991

continued ...



~~~.".,,"C"~~

fltl1l1; v:29


Colourless, oily, hygroscopic liquid with no Evaporation at 20'C is negligible: a harmfulodour. concentration of airbome particles can,Chemical Dangers: however, be reached quickly by spraying.

On combustion, forms toxic fumes (sulphur Effects of Short Term Exposure:

oxides). Upon heating, toxic fumes are formed. The substance is very corrosive to theT.he subst~nce is a str?ng oxidant a~d reacts eyes, the skin and the respiratory tract.vlolen~ly wllh combustible .and reduclng.. Corrosive on ingestion as weil. Inhalationmaterlal.s. The su.bstance IS a s~rong acld -II of an aerosol of this substance may causereacts vlolently wllh bases ~nd IS corrosive to lung oedema (see Notes).most common metals, formlng a flammablegas (hydrogen: see ICSC#OOO1). Reacts Effects of Long. Term or Repeatedviolently with water and organic materials with Exposure:evolution of heat.

Lungs may be affected by repeated orOccupational Exposure Limits: prolonged exposure to an aerosol of thisTLV 1mg/m3 (as TWA), 3mg/m3 (as STEL) substance. Risk of tooth erosion upon(ACGIH 1988-1989). repeated or prolonged exposure to anR t f E aerosol of this substance.8 ou es 0 xposure:

The substance Gan be absorbed into the bodyby inhalation of ils aerosol and by ingestion.

Physical Boiling point (decomposes) , 340°Cproperties Melting point 1 O°C

Relative density (water = 1) 1.8Solubility in water miscibleVapour pressure Pa at 146°C 0.13 -,Relative vapour density (air = 1) , 3.4

Environmental Possible harmful effects to aquatic life due to acidity.data

Notes The symptoms of lung oedema often do not become manifest until a few hours have passed andthey are aggravated by physical effort. Rest and medical observation is therefore essential.Never pour water into this substanœ: wh en dissolving or diluting, always add it slowly to thewater. Store in an area having corrosion resistant concrete floor.Transport Emergency Gard: TEC(R) -10bNFPA Code: H3, FO, R2, W

Additional8 information

ICSC: 0362 @ CEC, IPCS, 1991 Sulphuric acid

LEGAL NOTICE Neither the CEG nor the IPCS nor any persan acting on behalf of the CEG or the IPCS isresponsible for the use which might be made of this information.

This Gard contains the collective views of the IPCS Peer Review Committee and may not reflect in ail cases ailthe detailed requirements included in nationallegislation on the subject.

The user should verity compliance of the cards with the relevant legislation in the country of use.


.-,ill"' cc"""",,,"',,"c,",.'c


5.4.4 Life cycle of lead-acid batteries and lead )

l n this exercise, you are asked to draw the life cycle of lead-acid batteries and oflead. The purpose of the exercise is to understand the differences between aproduct

life cycle and a materiallife cycle.

Depending on the amount oftime available, you The exercise is best done in small groups (2-4may want to ask broader questions, such as what persons), with half of the groups developing themining activities are involved, how big is the lire cycle of lead-acid batteries, and the other halfwaste stream involved, how many products are the lire cycle of lead. The trainer will have tomade of lead, how much energy is used for lead- give continuous assistance as to how detailed theacid battery production, how much pollution does lire cycle should be.this involve, how much lead is recycled and how, To facilitate the exercise, it is advisable to useetc. This may require considerable literature either blackboard or a flipchart for drawing thestudy, so the trainer may want to collect some lire cycles.data and background material in advance. Some A recent UNEP publication on Life Cycleuseful background material is attached. UNEP Assessment would make useful preliminaryIE's Industry and EnvironmentNos. 2 and 3 of reading, and give further ideas for exercises and1994 focus on recycling. You may find these projects.issues useful for this exercise.

i~.1 ~~~~.J~~~~ll!~'J~

ReCYCling plays an important rote in the product, focusing on ail constituents of theconcept of sustainable development, and product, or you can look at the recycling of a raw

especially the recycling ofnon-renewable material, focusing on ail its applications.resources. This becomes clear when looking at When talking about recycling lead, you need tothe definition of sustainable development: a look at aIl the stages of the lire cycle of lead:development that meets the needs of the present from mining through refming, up to manufacture,generations without compromising the ability of consumption and disposai of the products infuture generations to meet their own needs. which lead is used.Recycling of materials and products aims to When talking about recycling lead-acidreduce the environmental impacts ofthese batteries, you need to look at ail stages of the lirematerials and goods, and to reuse resources. cycle of lead-acid batteries. That means you start

If we don't recycle lead but let it disperse in the at the excavation and production of itsenvironment, this resource will eventually be constituents: lead, sulphuric acid, PVC,exhausted. antimony, tin, etc., and you finish with the

There are two approaches when looking at recycling and/or disposaI of the differentrecycling. You can look at the recycling ofa components of the lead-acid battery.


Part 5 .Training Materia!

""'""--

r~.i v:31

8 r:.1~~I~~~::l'L=I~ill~

Read the background paper below, on Analytical tools for identifying Cleaner Production

opportunities. This paper is taken from the United Nations lndustrial Development Organization

(UNIDO) Training Course: Ecologically Sustainable Indus trial Development.

Divide the participants in two groups (depending on the number of participants you can divide the

participants into groups of 2, 4, or 8).

Group 1 Ensure that every phase from production or extraction ofPVCs (and its raw materials), lead,

sulphuric acid (and their raw materials), polypropylene (and its raw materials), and the production of

the other constituents is visible in the drawing.

Group 2 Design the lire cycle of lead. Ensure that every phase, from mining to disposaI, is visible in

the drawing. Name the different products in which lead is used, but don't describe the other resources

needed to make the product, e.g. when describing the use of lead in gasoline, don't include oil

refining in the drawing. Remember that lead is also used as a component of other chemical

substances, e.g. in pesticides, or ilS oxides.

8Use the background materials in the attachments and those provided by the trainer to understand the lire

cycle, and use the data in these documents to design your lire cycle oflead. Use Figure 5.10 as an

example ofhow a drawing of the lire cycle could look.

Figure 5.10 The life cycle

emissions

Production products ..ConsumptionProcess Process

wastes

product productprimary secondary wastes wastes

8aste Managemen

\. .( wastes ~ '/

/' , Earth /' ,mining and cultivation dispersion and immobilisation

8 ::'c"jj!!:A Workbook for Trainers: Environmental and Technologicallssues related to Lead-Acid Battery Recycling

'" ",.~""",'c,.."d", """"'00.,,",.'."""."-


"After drawing the life cycle, prepare a presentation, explaining the life cycle of the chosen subject. After )

the presentation, a plenary discussion could be initiated, raising some of the following questions:

.What information is missing from the drawn life cycle in order to be able to decide whether recycling

of lead/lead-acid batteries is beneficial for the environment?

.How tan life cycle analysis be useful for deciding on the benefits of recycling a product?

.How tan or should 'environmental costs' be incorporated in calculating the true costs of a product?

Recommended literature

Life Cycle Assessment: what it is and how to do Geneva: World Health Organization,

it [1996] Paris, France: United Nations International Agency for Research on Cancer.

Environment Programme, Industry and IRPTC Data Profile on: Lead [1990] Geneva:

Environment Centre. International Registration ofPotentially Toxic

Environmental Aspects of Selected Non-ferrous Chemicals, United Nations Environment

Metals (Cu, Ni, Pb, Zn, Au) Ore Mining: A Programme (IRPTC/UNEP).

Technical Guide [1991] Technical Report Risk Reduction Monograph No. 1: Lead

Seri es No. 5. Paris, France: United Nations Background and National Experience with

Environment Programme, Industry and ReducingRisk [1993] Paris: Organization for

Environment Centre. Economic Co-operation and Development,

IARC Monographs on the evaluation oft/le Environment Directorate.

carcinogenic risk of chemicals to humons: World Directory: Secondary Lead Plants [1994]

Some Metallic Compounds [1980] Volume 23. Fifth edition. London: International Zinc and

Lead Study Group.

r;.'[{;~l:03I~lli~:;il[\:-~ Li::.] LJii1::; ~~:'::;il03~-:~:; :.:., Li~:; ~i!ir;] ~~ :03[1::; :.:ii 11[:;~_l~cr.:..':03!r;1 i~:-JLU:; I:;~'J ~Ji.iir;: il::;:-Jr;::

Analytical tools for identifying Cleaner Production opportunities: Reading Excerpts

Identifying and setting boundaries for life,cycle stages

T he quality of a lire-cycle inventory depends on an accurate description of the system to be

analyzed. The necessary data collection and interpretation is contingent on proper understanding

of where each stage of a life cycle begins and ends.

General scope of each stage

Raw materials acquisition Manufacturing

This stage of the life cycle of a product includes The manufacturing stage produces the product

the removal of raw materials and energy sources or package from the raw materials and delivers it

from the earth, such as the harvesting oftrees or to consumers. Three substages or steps are

the extraction of crude oil. Transport of the raw involved in this transformation: materials

materials from the point of acquisition to the manufacture, product fabrication, and

point ofraw materials processing isalso filling/packaging/distribution.

considered part ofthis stage.



lili v:33

8 Materials manufacture: This step involves Use/reuse/maintenance

converting raw material into a form that can be This is the stage consumers are most familiarused to fabricate a finished product. For with: the actual use, reuse and maintenance of the

example, several manufacturing activities are product. Energy requirements and environmentalrequired to produce a polyethylene resin from wastes associated with product storage andcrude oïl. The crude oïl must be refined; consumption are included in this stage.ethylene must be produced in an olefins plantand then polymerized to produce polyethylene; Stages of a life cycletransportation between manufacturing activities .Raw materials acquisition

and to the point of product fabrication is .Manufacturingconsidered part of materials manufacture. -materials manufacture

Product fabrication: This step involves -product fabrication

processing the manufactured material to create -filling/packaging/distributiona product ready to be filled or packaged; for .Use/reuse/maintenance

example, blow moulding a bottle, forming an .Recycle/waste managementaluminium can, or producing a cloth diaper.

Fillillglpackingldistribution: This step includes Recyc/e/waste management8 aIl manufacturing processes and transportation Energy requirements and environmental wastes

required to fill, package, and distribute a associated with product disposition are includedfinished product. Energy and environmental in this stage, as weil as post-consumer waste

wastes caused by transporting the product to management options such as recycling,retail outlets or to the consumer are accounted composting, and incineration.

for in this step of a product's lire cycle.

Issues that apply to ail stages

The following general issues apply across ail four use of fuels in transport vehicles or process

lire-cycle stages: operations.Energy and transportation Waste management practices

Process and transportation energy requirements Depending on the nature of the product, a

are determined for each stage of a product's lire variety ofwaste management alternatives may becycle. Some products are made from raw considered: landfilling, incineration, recycling,materials such as crude oïl, which are also used and composting.as sources of fuel. Allocation of waste or energy

8Use ofthese raw materials as inputs to products among primary and co-products

represents a decision to forego their fuel value. Some processes in a product's lire cycle mayThe energy value of such raw materials that are produce more than one product. ln this event, ailincorporated into products typically is included as energy and resources entering a particular processpart of the energy requirements in an inventory and ail wastes resulting from it are allocatedanalysis. Energy required to acquire and process among the product and co-products. Allocation isthe fuels burned for process and transportation most commonly based on the mass ratios of theuse is also included. products, but there are exceptions to this.Environmental waste aspects Summing the results of each stage

Three categories of environmental wastes are To calculate the total results for the entire liregenerated from each stage of a product's lire cycle of a particular product, the energycycle: atmospheric emissions, water-borne requirements and certain emission values for eachwastes, and solid wastes. stage of the product's lire cycle can be summed.

These environmental wastes are generated by For example, energy requirements for each stageboth the actual manufacturing processes and the are converted from fuel units to million British

8 A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling


,Thennal Units (BTUs) or megajoules and basis. Claims for confidentiality should be made ,1

summed to fmd the total energy requirements. only when it is reasonable to expect that releaseSol id wastes may be summed in pounds or of the infonnation would darnage the supplier's

converted to volume and summed. The current, competitive position. Even then, the data inputs

preferred practice is to present the individual to an extemal use are legitimately expected to beenvironmental releases into each of the independently verified.environmental media on a pollutant-by-pollutant A peer review process leading to agreed-upon

basis. Where such specificity in an extemal study reporting is one possible mechanism for dealingwould reveal confidential business infonnation, with this issue. Other approaches for independentexceptions should be made on a case-by-case verification are possible.

Table 5.5 Recyclable/non-recyclable applications for lead

Rec clable Non-rec clable

Batteries Gasoline additives :i

Roofin Iflashin s Glass

Pi es Plastics stabilizers

Gable sheaths Shot-ammunition

Radiation shieldin Paint i ments

Window trames Solders

Yacht keels Geramic lazes

Wheel wei hts

Table 5.6 Recovery of lead products

Product Product Recove

Batteries:auto~obile -90 3-4 }traction -100 4-6

stationa -100 u ta 10Sheet 90-95 50-100Pi e 70-80 50-100Gable sheathin 50 40

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Tra;ners )


.,..,

HIa v:35

8Table 5.7 Battery recycling rates in some OECD countries

1986 1987 1988 1989 1990 1991

Australia 90

Belgium 77

Canada 93

France 80 90

Germanv FR 83 >95

Italy 83

Japan 92.3 92.5 95.2 93.8 92.2

Spain 83

Sweden >100e

United Kingdom 84 93

United States 88.6 91.0 95.3 97.7e = estimated.

8 Note: Methods used to detennine rates may vary by country. Recycling rates tan exceed 100 per centwhen stored or stockpiled batteries are returned.

Sources: Country comments, ILZSG, Commission of the European Communities, Battery CouncilInternational, US Department of Commerce, US Bureau of Mines, Japan Storage Battery Association,Tonatsu Metallurgical Company.

Source: Proceedings of the REC '93 International Recycling Congres s, "Advances in Recovery andRecycling. Concepts and technology."

8

8 cC;:A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling


')Table 5.8 Summary tables: lead C

total reported consumption by country

Thousand Metric Tonnes1988 1989 1990 1991 1992 1993 % change

1992.3Australia 49.3 51.7 46.0 42.6 43.1 51.2 18.8Austria 61.0 61.0 65.5 66.0 66.0 62.0 -6.1Sel ium 66.1 62.0 67.7 63.5 64.5 66.0 2.3Srazil 95.5 100.3 75.0 66.0 69.0 74.0 7.2Canada 88.0 87.7 71.5 79.6 91.7 89.1 -2.8

.12.1 13.2 13.4 12.2 7.0 4.0 -42.9238.2 265.4 263.2 266.3 259.4 240.2 -7.4336.9 366.2 375.3 401.0 397.5 362.4 -8.851.1 52.9 51.8 53.6 40.2 33.9 -15.7

252.0 261.0 259.0 259.0 247.0 234.0 -5.3406.5 405.7 416.4 422.2 401.3 371.2 -7.5 )

blic of 146.0 155.0 149.0 164.0 164.0 178.0 8.5Mexico 77.1 85.7 66.8 79.7 92.5 84.0 -9.2Netherlands 58.4 58.5 62.0 59.0 52.0 48.0 -7.7NewZealand 7.6 10.0 8.0 5.1 5.1 6.7 31.4*** Scandinavia 58.4 41.8 36.3 33.0 33.0 41.0 24.2

South Africa 56.1 62.9 65.9 53.9 53.9 52.7 -2.2**** South East Asia 171.4 172.0 185.0 237.0 237.0 253.0 6.8

Sain 110.9 110.0 126.7 105.0 105.0 104.0 -1.0i z 10.7 7.9 8.7 7.6 7.6 7.5 -1.3

dom 339.5 336.4 334.0 302.3 302.3 298.0 -1.2s 1245.2 1277.6 1275.2 1240.7 1240.7 1357.1 9.4

Total 3924.8 4044.9 4022.4 4027.7 3979.8 4018.8 1.0

* Prior to 1991, former Federal Republic only** Consumption in the Organised Sector

*** Denmark, Norway and Sweden**** Taiwan (China), Hong Kong, Philippines, Malaysia, Singapore, Thailand and lndonesia

t Data for these countries include total metal consumption in ail forms, i.e. refined lead andalloys (lead content), plus remelted lead recovered from secondary materials. Data for other

countries include refined lead and alloys only

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers -'Part 5 .Training Materia!

r v:37

8Table 5.9 Summary tables: lead

principal uses

LEAD CONSUMPTION: THOUSAND METRIC TONNES

1988 1989 1990 1991 1992 1993 % change

1992.93

Batteries 2394.3 2492.3 2541.3 2557.8 2565.6 2661.7 3.7

Gable sheathinq 183.2 196.0 182.1 169.9 152.5 143.5 -5.9

Rolledandextruded 312.0 311.8 309.6 284.9 273.2 265.4 -2.9

fJroducts

Shot-ammunition 93.8 98.8 101.3 108.8 113.2 115.4 1.9

Alloys 147.1 141.8 134.4 133.8 139.0 137.8 -0.9

Pigments and other 526.6 557.0 517.0 542.9 530.6 488.9 -7.9

comfJounds

Gasoline additives 103.0 98.2 86.9 74.0 58.1 54.3 -6.5

8 Miscellaneous 164.8 149.0 149.8 155.6 147.6 151.8 2.8

Total- 3924.8 4044.9 4022.4 4027.7 3979.8 4018.8 1.0

PERGENTAGES OF TOTAL GONSUMPTION

1988 1989 1990 1991 1992 1993

Batteries 61.0 61.6 63.2 64.0 64.5 66.2

Gable sheathing 4.7 4.8 4.5 4.2 3.8 3.6

Rolled and extruded 7.9 7.7 7.7 7.1 6.9 6.6

fJroductsShot-ammunition 2.4 2.5 2.5 2.7 2.8 2.9

Alloys 3.7 3.5 3.3 3.3 3.5 3.4

Pigments and other 13.4 13.8 12.9 13.5 13.3 12.2

comfJoundsGasoline additives 2.6 2.4 2.2 2.1.8 1.5 1.4

Miscellaneous 4.2 3.7 3.7 3.9 3.7 3.8

Total- 100.0 100.0 100.0 100.5 100.0 100.0

8 * Countries included: Australia, Austria, Belgium, Brazil, Canada, Finland, France, Germany, lndia,

ltaly, Japan, Republic of Korea, Mexico, Netherlands, New Zealand, Scandinavia, South Africa, South

East Asia, Spain, Switzerland, United Kingdom, United States.

8 :A Workbook for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

",0"


"-

5.4.5 Comparison of lead-acid battery recycling technologies )

T his exercise requires a considerable amountof work, and is therefore best clone by NOTE

students with a technical background who have The result of this exercise should flot state a

thoroughly studied the background papers. The preference for one technology over the other.exercise should be tackled as a project, on which The comparison of the different technologies

students are allowed to work in small groups over should reveal thatthey can not easily be

a period of several weeks. It is advisable to compared with each other because of factors likeorganise this project in advance, and maybe gel accessibility of the market for recycled products,the involvement ofsome senior students to assist capacity of the technology, local conditions, etc.

the working groups. The students may need However, you can identify the environmentalconsiderable guidance from the trainer as to how impacts of the different technologies and developdetailed the study should be. It"requires close general areas for preferences.

involvement of the trainer.

")

There are various types oflead-acid battery recycling facilities, ail using a range of technologies andtechniques. As a consequence, the end products and their quality differ depending on the facility wherethe lead-acid batteries are recycled. End products may vary from scrap and secondary lead, to reusab.1e

polypropylene, detergents, refined lead, etc.

The recycling facilities mainly differ from each ailier in two respects:

1The wrecking section of the lead-acid battery recycling facility.The simplest wrecking operations are designed to release only the sulphuric acid. The most

advanced wrecking operations separate and recover ail the constituents of the battery: acid, PVC,ebonite, polypropylene, lead scrap, and lead paste. ln between, there is a range ofwrecking operations

using different technologies and resulting in different end products (see background papers).

2The smelting section of the lead-acid battery recycling facility.The International Lead and Zinc Study Group distinguishes the following smelter types: blast

fumace, stationary reverberatory fumace, blast fumace and stationary reverberatory fumace, bergsoetype plant, electric fumace, blast fumace and electric fumace, stationary reverberatory fumace and

electric fumace, Kivcet, and lsasmelt process (World Directory, ILZSG, 1994).

This exercise consists oftwo assignments. The first assignment asks you to make an environmentalevaluation ofseveral types ofwrecking operations. The second assignment concems the selection of themost environmentally friendly smelter type. You are asked to choose one of the assignments.

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Warkbaak for Trainers -"


~il'lnrn~'1Wg,tr:,îilt;JI"1 v. 39"~~;f4w"[".,,,,;! ;Jl'"""":;,!;!"",,, .

8 r~~~~~i~1 ~'j=~.II1

Y OD are asked to make an evaluation of method of comparing the technologies. Use

existing wrecking ope rations with respect to criteria for capacity, capital investment, energytheir general and environmental performance. consumption, emissions, end-products,Find literature in specialized libraries or ask for environmental impacts, occupational health, etc.information about specific wrecking operations at Prepare a presentation of the different wreckingthe patent office. Compare two or three wrecking operations you studied against the criteria youoperations, based on a thorough study. At the developed, and give an indication of thesame time you will have to develop a structured environmental impacts of each of the operations.

r;'~~~~~!I~l!I=~!11 ~~

8 Y OD are asked to make an evaluation of develop a structured method of comparing theexisting lead smelting technologies with technologies. Use criteria for capacity, capital

respect to their general and environmental investment, energy consumption, emissions, end-

performance. products, environmental impacts, occupationalFind literature in specialized libraries or ask for health, etc.

information about specific smelting technologies Prepare a presentation of the different smeltingat the patent office. 8ased on a thorough study, technologies you studied against the criteria youcompare two or three smelting technologies, developed, and give an indication of thewhich are also considered by the International environmental impacts of each of theLead and Zinc Study Group. You will have to technologies.

8

8 Il'

A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

.Jo"""'",""""".""","'",,


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5.5 50me suggestions for answers )

5.5.1 Obstacles to a perfect recycling scheme

Question 1 (a) Neglect, lack ofawareness of a collection system, the distance to the collector, andthe lack of an (economic) incentive may ail contribute in preventing consumers fromdelivering lead-acid batteries to the retailer, collector or drop-off depot.

(h) Keeping the batteries 'in-house' for a long time may lead to inappropriate disposaiof the lead-acid batteries; risks to playing children. Inappropriate storage may lead toaccidental breaking of the battery.

Question 2 (a) The constraints include neglect, distance to the battery breaker, and absence ofeconomic incentives (internationallead-prices or deposits). These constraints mayact in combination with the possible absence of a battery breaker or secondary lead-smelter in the country. ln this case, international regulations, geographical distanceand cost-benetit oftransportation play an important foie.

(h) Leaking of sulphuric acid onto the ground, leading to soil contamination. Exposureofworkers to acid and lead when inappropriately stored. Depending on the locationof the storage facility, animais and children may corne in contact with the batteries,leading to exposure to toxins. With rime, there is an increased probability ofdegradation of the stored batteries because ofexposure to the elements, vandalism,and accidents (such as tire). The more batteries that are stored, the more serious theconsequences of leaks.

Question 3 (a) Decline in internationallead-prices. Distance to secondary lead-smelter incombination with the cost-benetit oftransporting a small number oflead-acidbatteries (see answer to Question 2a). Note the problem which arises when lead losesits value.

(h) See answer to Question 2b.

5.5.2 Case-study on a lead-acid battery recycling facility

Question 4 (a) When sulphuric acid is allowed to enter the rotary furnace, it causes SO3emissions. If the sulphuric acid is removed, less energy is needed to smelt the leadfractions. Sulphuric acid can also be recycled cost effectively.

(h) The main environmental problem is the formation of acid Tain.

(c) PbSO4 + Na2CO3 ~ PbCO3 + Na2S04See 3.4.4 Low waste technology for reprocessing ballery scrap in Part 3: TechnicalBackground Pa pers for an explanation ofwhy the lead paste is desulphurized beforethe smelting process.

Question 5 1 Weight of used lead-acid battery * fraction of constituent = kg constituent.

Question 6 1 See International Chemical Safety Cards, under acute hazards/symptoms, prevention,and effects of long term or repeated exposure.



rè:iEl; v:41

8 Question 7 Fuel consumption draps from 90kg to 40kg peT tonne of scrap. Waste gas draps from

12m3 to 3.2m3/kg fuel. Maximal dust content in cleaned gas is 2.5mgiNm3. Dustcontent draps from 50% to 35%.

Reduction of lead in dust peT tonne scrap can be calculated as follows:(1- (40 kg * 3.2m3/kg * 2.5mg/Nm3 * 0.35)/(90kg * 12m3/kg * 2.5mg/Nm3 * 0.5» * 100%

= 91.7%

Question 8 During wrecking operations, 95% of the sulphuric acid is removed, and lime is added

to neutralize the residual acid in a ratio of 1.2: 1 on a weight basis. Total weight afterwrecking section:

1 million batteries/year * 17.2kg/battery 17,200 tonnes of batteries/yearRemoved sulphuric acid = 0.24 * 17,200 * 0.95 3921.6 tonnesAdded lime = 0.05 * 17200 * 1.2 " 1032 tonnes

Total battery scrap after wrecking operations is:17200 -3 921.6 + 1 032 14 310.4 tonnes

Input for smelting section consists of 85% from wrecking section, 10% dust and

8 recycling products, and 5% reagents. Total input in rotary fumace is 16 835.8 tonnes.Therefore, the average load of one rotary fumace is:

16835.8/(5 * 5 * 42 * 2) = 8 tonnes

Question 9 You may want to use the example of the secondary lead smelter given in 3.4.4 Lowwaste technology for reprocessing battery scrap in Part 3: Technical BackgroundPapers. One of the exercises in Part 5 focuses on the different wrecking techniques.You may want to do that exercise flrst.

Question 10 (a) The fraction oflead in the rotary fumace will increase. Based on an average

capacity of each load of 8 tonnes, the capacity of the plant will increase.

(h) The energy consumption may be lower because the plastics are not used as an

energy source anymore.

Question 11 (a) The risks oftransportation (accidents, but also spilling of lead-acid from trucks

passing through urban areas). Wastewater containing lead, sulphuric acid and otherheavy metals may be discharged into the surface water with inappropriate treatment.

8 Lead emissions during smelting, refining, and ingotting -either through air, water,or crops (see transparency on exposure pathways in Section 3.3). Due to sprinklingof the site to prevent the formation of lead dust, the soil may become contaminatedwith lead.

(h) During malfunction/accidents, the afterbumer and emission contrai equipment maynot be able to retain pollutants like sulphuric acid fumes, lead, and SO3, and dioxins

may be formed due to incomplete buming.Students were asked to investigate the risks associated with each of the

constituents of the lead"acid battery as part ofPreliminary Exercise 3. Theconsequences of emissions from secondary lead smelters for human health are alsosummarized in 3.2.1 Environmental agency closes down company alter finding leadin human blood, cows' meat; 3.2.2 Potential environmental and occupational hazardfrom lead; and 3.2.3 Mechanismsfor risk reduction oflead in the European

Community, in Part 3: Technical Background Pa pers.

8 ;;A Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling


,Question 12 (a) Slags can be used as construction material- for road foundations, etc. )

(h) The major drawback may be that the heavy metals are not immobilized enough andstart leaching, causing soil pollution, or leading to health problems in the buildingswhere they are used.

Question 13 There are several possibilities, including using it to preheat the scrap before it enters

the smelter; it can also be used to generate energy/electricity, or for heating

surrounding buildings.

Question 14 The concentration in the air should always be below 0.05gim3. That means that the

ventilation system should be able to remove as much lead dustltime unit as is beinggenerated by the two rotary fumaces. The ventilation system should be able to reach asteady state with a lead concentration in the air of 0.05 (gim3).

QI = flow of dust from smelter (lm3/h).Q2 = flow being ventilated (unknown/h).

Q3 = flow without lead going into the hall = Q2 -QI.CI = concentration lead dust in QI = 60 (gram/m3).CI = concentration lead dust in the hall (gim3).C3 = 0 (gim3).V = volume of the hall = 3600m3.t = time (h).

When time reaches infmity, CI should remain 0.05gim3.The concentration at t = 0 is 0 (gim3).

This leads to the following equations:

dCV-1- = QICO -Q2Ct +Q3C3

dt

In(QICI -Q2Ct) -dt---Q2 V

1 -tQ2Ct = -(QI CI- exp(- + In(QICI)))

Q2 V

For t ~ 00, CI reaches 0.05 (g/m3). This leads to the following equation:

Ct = -9l CIQ2

From this, it follows that the ventilation capacity Q2 = 1200m3/h.



" " "-"_.~." """--".""""'.."_.

.;i v:43

8 Question 15 Frequent cleaning of areas contaminated with lead, using methods which do not

spread the lead, such as mobile or fixed vacuum cleaning apparatus with highefficiency filters or wet cleaning methods.

Isolate eating and changing areas from areas of lead work and provide suitablefacilities to store food, drink and smoking materials.

Do not allow smoking, drinking or eating in work areas.Washing ofhands and removal of contaminated clothing before entering eating area.Provide work clothing which can be kept separate from normal clothes.Removal of contaminated clothing and showering prior to leaving the workplace

premises.Washing of contaminated clothing at the workplace, so as to minimise the likelihood

of spreading the contamination to the home.Make sure that personal protective equipment is properly maintained and stored.Set procedures for regular plant maintenance.Follow operation instructions closely in order to avoid lead dust dispersion during

various batch and transfer operations.

8 Question 16 Don't use PVC, because it is not being recycled. Try to use other materials so slagsdo not contain heavy metals. Design batteries so that they can be repaired rather than

recycled.The use ofPVC separators results in considerable economic and technical problems

(difficulties in dust collection, equipment corrosion, necessity of special storages, etc.)during scrap treatment. Replacing these separators with ones which do not containchlorine cuts the costs for lead production from secondary raw material.

At the same time, the use ofnew parts in lead-acid batteries complicates the scraptreatment. For example, the use of copper contact pins instead of lead can make scrapseparation difficult, and increases the yield of drosses and matte. The most seriousdifficulties can be caused by addition to lead alloys of such elements as cadmium,tellurium, or arsenic. These elements and their compounds are more volatile and toxicthan lead and its compounds.

Question 17 97.2% of alllead is recycled. Assume that 97.2% of metallic lead and 97.2% of leadfrom lead paste is being recuperated. Calculate the fraction of lead in lead paste, thencalculate the total initial amount of molecular lead. 97.2% of this total can be used for

8 production of new batteries.

80 .

1

Appendices~

~..c:~, ~

~,~,~~ Jffc;;;; 7~

UNEF

Appendices

"

1 Supporting Documents for this Package 3

II List of Training Resource Packages available from UNEP lE 5

III About UNEF Industry and Environment 7

t

lA Warkbaak for Trainers : Environmental and Technologicallssues related to Lead-Acid Battery Recycling

",,-," """ 3

Appendices

8Appendix 1

Supporting Documents for tbis Package

The following documents are available to support further work using this package:

8 Promoting Waste Recycling: Part 1 [1994]ln lndustry and Environment Vol. 17, No. 2.

Promoting Waste Recycling: Part 11 [1994]ln lndustry and Environment Vol. 17, No. 3.

Gestion de l'environnement dans les usines de recyclage des batteries plomb-accide[anticipated publication date 1996] UNEP lE.

Life Cycle Assessment: what it is and how to do it [1996] UNEP.

8

8A Warkbaak for Tra;ners: Environmental and Technologicallssues related to Lead-Acid Battery Recycling

--~-,...'".

4 United Nations Environment Programme' Industry and Environment

"

}

)

)

Environmental and Technologicallssues related to Lead-Acid Battery Recycling : A Workbook for Trainers )

Appendices

..." '"Co

5

Appendices

8Appendix II

List 01 Training Resource Packagesavailable Irom UNEP lE

T he following training resource packages have been developed by UNEP lE. They aIl useinteractive training methodologies to explain the subject, and are aimed at educators who,although technically skilled, may not have specialized knowledge in ibis particular area.

The packages are available from UNEP lE.

Some trainers' packages are still under development, and users are encouraged to assist UNEP to8 bring these to a fmal stage of publication.

Due to the cost ofprinting of the packages (between 100 and 400 pages), the completed documentsare offered for sale to most users. However, a limited number of draft packages are free of charge tousers prepared to contribute to their further development through review, field testing and addingmaterial. Assistance with translation would also be welcome.

Cleaner Production: a Training Resource exercises. 110 pages. Price $120. This packagePackage [1996] First Edition. Contains also helps to explain the APELL programme.background reading, transparencies, Risk Management ofContaminated Industrialbibliography, and work exercises. 110 pages. Land: a Training Resource Package [1996]Price $120 (English, Spanish). This package First Edition. Contains background reading,can be used with the workbooks below. case studies and work exercises. 110 pages.

Trainer 's Workbook on Cleaner Production in Price $120. English, Spanish.Leather Tanning [1996] First Edition. Contains Hazardous Waste, Policies and Strategies: abackground reading, case studies, work Training Manual [December 1991] TRIO.

8 exercises and answers. 120 pages. Price $120. Contains background reading, case studies,Trainer 's Workbook on Cleaner Production in work exercises, reference tables andthe Brewing Industry [1996] First Edition. bibliography. 250 pages. Price $120. English,Contains background reading, case studies, French, Spanish.work exercises and answers. 75 pages. Landjill of Hazardous Industrial Wastes: aPrice $100. Training Resource Package [March 1994]

Trainer 's Workbook on Cleaner Production in TR 17. Contains background reading, caseTextile WeI Processing [August 1995] First studies, work exercises, reference tables andEdition. Contains background reading, case bibliography. 315 pages. Price $120.studies, work exercises, answers, references. Environmental and Technological Issues140 pages. Price $120. related to Lead-Acid Battery Recyc/ing:

Management of Industrial Accident Preventioll Trainers Worbook [1996] First Edition.and Preparedness: a Training Resource Contains background reading, transparencies,Package [1996] First Edition. Contains bibliography and work exercises. 130 pages.background reading, case studies and work Price $120.

8A Workbook for Trainers: Environmental and Technologicallssues related to Lead-Acid Battery Recycling

"'"' _."", '

6 United Nations Environment Programme' Industry and Environment

-.,

Environmental Management of Mining Sites: a Training Manual on Chillers and Refrigerant c)Training Manual [1995] UNEP/DDSMS. Management [1994] Price FF425/us$85 forContains background reading, transparencies, developed countries.case studies, work exercises and answers. Training Manual on Good Practices in200 pages. Price $160. Refrigeration [1994] Price FF400/US$80 for

Environmental Management Systems: Training developed countries.Resource Kit [1995] UNEP/ICC/FIDIC. Environmental Impact Assessment: a trainingContains background reading, transparencies, resource manual [1996] Preliminary version.case studies, work exercises, bibliography. A vailable from UNEP Environment and492 pages. Price $190. Economics Departrnent, UNEP, Nairobi.

Aerosol Conversion Technology Handbook [1994]Price FF225/us$45 for developed countries.

Enquiries UNEP lETour Mirabeau39-43 quai André Citroën75739 Paris Cedex 15France

Tel 33 (1) 44 37 1450Fax 33 (1) 44 37 1474Email [email protected]

http://www .unepie.org/home.html

!


Appendices

7

Appendices

8Appendix III

About UNEP Industrv and Environment

I ndustry and Environment was established by UNEP in 1975 to bringindustry and government together to promote environmentally sound

industrial development.

8 UNEP lE is located in Paris and ils goals are to: the transfer of infonnation and the sharing of1 encourage the incorporation of environmental knowledge and experience, UNEP lE bas

criteria in industrial and development plans; developed three complementary tools:2 facilitate the implementation of procedures and .technical reviews and guidelines;

principles for the protection of the environment; .Industry and Environment: a quarterly review;3 promote the use of safe and clean technologies; .a technical query-response service.4 stimulate the exchange of infonnation and ln keeping with ils emphasis on technical

experience throughout the world. cooperation, UNEP lE facilitates technologyUNEP lE provides access to practical transfer and the implementation of practices to

infonnation and develops co-operative on-site safeguard the environment through promotingaction and infonnation exchange backed by awareness and interaction, training and diagnosticregular follow-up and assessment. To promote studies.

Some relevant UNEP lE publications

Refer to Appendix Ilfor trainers' packages. For comp/ete /ist, refer to publications catalogue.

Industry and Environment [quarterly] deals with Energy, Efflciency and Climate Change [1991]8 issues relevant to industrial development, such UNEP/IPIECA. 95pp.

as auditing, waste management, industry- Hazard Identification and Evaluation in a Localspecific problems, and environmental news. Community: Technica/ Report No. /2 [1992]

Government Strategies and Policies for Cleaner 86pp.Production [1994] 32pp. Hea/th Aspects ofChemical Accidents:

Cleaner Production Worldwide Vol. 1 and Il guidance on chemical accident awareness,[1995] 48pp. preparedness and response for health

Life Cycle Assessment: what it is and how to do professionals and emergency respondersit [1996] 92pp. Technica/ReportNo. 19 [1994] A joint

Audit and Reduction of lndustrial Emissions IPCS/OECD/UNEP/WHO publication: OECDand Wastes: Technica/ Report No. 7 [1991] Environment Monograph No. 81. 47pp.UNEP/UNIDO. 127pp. Environmental Aspects of lndustrial Wood

Monitoring of lndustrial Emissions and Wastes: Preservation: a technical guide Technica/Technica/ReportNo. 27 [1996] Report No. 20 [1994] IO5pp.UNEP/UNIDO. 188pp. The Textile Industry and the Environment

Technica/ReportNo. 16[1994] 120pp.


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8 United Nations Environment Programme elndustry and Environment

îEnvironmental Management in the Brewing Company Environmental Reporting Technical !

Industry TechnicalReportNo. 33 [1995] 120pps. Report No. 24[1994] 118pp.Storage of Hazardous Materials Technical From Regulations to Industry Compliance:

Report No. 3 [1990] Building Institutional Capabilities TechnicalCampa/lies Organization and Public Report No. Il [1992] 62pp.

Communication on Environmental IssuesTechnicalReportNo. 6 [1991] 130pp.


Appendices

i

8

Evaluation FormEnvironmental and Technological Issues

related to Lead-Acid Battery Recycling

A s part of the continuing review ofthis trainers package, we would appreciate your cooperation inanswering the following questions. Please retum the completed evaluation form to:

UNEF lE, Tour Mirabeau, 39-43 quai André Citroën, 75739 Paris Cedex 15, FranceFax 33 (1) 443714 74.

1 Do you have any suggestions for improvement of the trainers package? How cou Id weimprove its readability, contents, practical use, and so on?

8

2 How was the package useful in preparing your own training activity?

83 Did the background information and the transparency set in Part 3 provide you with

enough information? What was missing?

continued ...

8A Workbook for Trainers : Environmental and Technologicallssues related to Lead-Acld Battery Recycllng

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