Characterization of Mobile Printed Circuit Board using Ammonium

Thiosulphate solution and analysis of key issues in implementation

of EPR strategy in Indian E-Waste Management System
Final Thesis report submitted to the

Indian Institute of Technology, Kharagpur

in partial fulfillment for the award of the degree of

of

Master of Technology
in

Environmental Engineering and Management

by

Ganesh Kumar

Roll No. – 15CE63R02

Under the supervision of

Dr. B. K. Dubey

Department of Civil Engineering,

Indian Institute of Technology, Kharagpur

April-2017
 CERTIFICATE

This is to certify that the thesis entitled “Characterization of Mobile Printed Circuit

Board using Ammonium Thiosulphate solution and analysis of key issues in

implementation of EPR strategy in Indian E-Waste Management System”,
submitted by GANESH KUMAR to Indian Institute of Technology, Kharagpur, for the
award of the degree of Master of Technology in Environmental Engineering and Management, is
a record to bona fide research work carried under my supervision and is worthy of consideration
for the award of the degree of Master of Technology of the institute. The contents embodied in
this thesis have not been submitted to any other university or institute for the award of any
degree or diploma.

Date: (Supervisor)

Place: Dr. Brajesh Kumar Dubey

i
 DECLARATION

I, GANESH KUMAR, hereby declare that the thesis entitled “Characterization of

Mobile Printed Circuit Board using Ammonium Thiosulphate solution and
analysis of key issues in implementation of EPR strategy in Indian E-Waste
Management System” submitted for the degree of Master of Technology in Environmental
Engineering and Management, is the record of work carried out by me under the guidance of Dr.
Brajesh Kumar Dubey and has not formed the basis for the award of any degree, diploma,
associate ship, fellowship and titles in this or any other university or institution of higher
learning.
I further declare that the material obtained from other sources has been duly acknowledged in the
thesis.

Date:
GANESH KUMAR

ii
 ACKNOWLEDGEMENT

I am grateful to my advisor, Dr. Brajesh Kumar Dubey, for his excellent support throughout
my academic career at the Indian Institute of Technology. He helped me get trained in various
facets of solid and hazardous waste management, always giving me opportunities to learn
something new. He has been a great source of inspiration and a role model. I am thankful for the
immense encouragement and financial support that he graciously provided during this study.
It is my privilege to express my gratitude to Dr. Partha Pratim Chakraborty, Director, IIT
Kgp; Dr. K. S. Reddy, HoD, Department of Civil Engineering; Dr. Anjali Pal, Faculty Advisor
for their constant support, encouragement, suggestions and for providing all technical facilities
throughout the project work. I would like to express my sincere gratitude to all the faculty
members of Environmental Engineering division and Civil Engineering for their encouragement
during the course for the past two years.
I expand my thanks to all non-teaching staff members of Civil Engineering department for their
support and concern through my project. Thanks to my friends and juniors for making my stay at
IIT memorable and without them the study would not have been successful.
Above all, I wish to extend my sincerest regards to my parents, relatives and family friends
whose well wishes and blessings have always played a key role in all the walks of my life.

Date: GANESH KUMAR

iii
Contents
INTRODUCTION ...................................................................................................................................... 10
1.1. General Introduction ........................................................................................................................ 10
1.2. Definition and Composition of E-waste........................................................................................... 12
1.3. Global E-Waste generations............................................................................................................. 14
1.4. Harmful Impacts of E-Waste on Human health ............................................................................... 15
1.5. Objectives ........................................................................................................................................ 16
LITERATURE REVIEW ........................................................................................................................... 18
2.1. Literature review of metal extraction processes................................................................................... 18
2.1.1. Classification of metal extraction processes. ............................................................................ 20
2.1.2. Hydrometallurgical processes ................................................................................................... 22
2.1.3. Thiosulphate leaching ............................................................................................................... 24
2.2. E-waste Management in Switzerland ............................................................................................... 28
2.2.1. Material and financial flows...................................................................................................... 29
2.2.2. Lessons from Switzerland E-waste management experience .................................................. 30
E-WASTE MANAGEMENT SYSTEM IN INDIA ................................................................................... 33
3.1. Existing E-Waste generation and management scenario in India .................................................... 33
3.1.1. E-waste trade in India ............................................................................................................... 35
3.2. Comparison of the two waste management systems ........................................................................ 35
3.3. Proposed Indian Electronic-waste management system .................................................................. 37
3.3.1. Material and financial flow ....................................................................................................... 38
3.3.2. Responsibility of various actors ................................................................................................ 39
METHODOLOGY ..................................................................................................................................... 45
4.1. Material and Methods ...................................................................................................................... 46
4.1.1. Collection of mobile phones ..................................................................................................... 46
4.1.2. Shredding of PCBs ..................................................................................................................... 49
4.1.3. Leaching of mobile PCBs ........................................................................................................... 49
4.1.4. Acid digestion of mobile PCBs................................................................................................... 50

1
 4.1.5. SEM-EDS Analysis ...................................................................................................................... 53
4.1.6. XRD-Analysis.............................................................................................................................. 53
4.2. Leaching of Mobile PCBs using Aqua Regia and Ammonium Thiosulphate ................................. 53
4.3. TCLP Test for Mobile PCB ............................................................................................................. 58
RESULT AND DISCUSSION ................................................................................................................... 60
5.1. Scanning Electron Microscopic Analysis (SEM) ............................................................................ 60
5.2. X-ray Diffraction Analysis (XRD) .................................................................................................. 62
5.3. Characterization of Mobile PCBs for Gold and silver ..................................................................... 62
5.3.1. Characterization of gold and silver elements in mobile PCBs using aqua regia (A mix of nitric
acid and hydrochloric acid in the molar ratio of 1:3).......................................................................... 62
5.3.2. Characterization of gold and silver elements from mobile PCBS using ammonium
thiosulphate, CuSO4 .5H2O andNH4OH ............................................................................................... 63
5.4. Analyzing toxic characteristics of gold leached solution by comparing heavy metal concentrations
in the solution with Toxicity Characteristic Leaching Procedure (TCLP) and Central Pollution Control
Board (CPCB) limits for hazardous material. ......................................................................................... 72
5.4.1. Results of TCLP Test .................................................................................................................. 75
5.5. Analyzing problems associated with implementing Extended Producer Responsibility based e-
waste management system in India. ........................................................................................................ 78
5.5.1. Indian E-Waste Management system waste generation .......................................................... 78
5.5.2. Hurdles in implementing EPR based E-Waste management systems in India. ........................ 84
5.5.3. Recommendations for setting up EPR based E-Waste management system........................... 84
SUMMARY, CONCLUSION AND FUTURE WORK ............................................................................. 87
6.1. Summary and conclusion ................................................................................................................. 87
6.2. Directions of Future work ................................................................................................................ 89
REFERENCES ........................................................................................................................................... 90

2
 LIST OF TABLES

Table1 Definitions of E-Waste along with their references……………………………………...13

Table2 Quantity of valuable metals and toxic substances (in million tons) present in E-Waste
produced globally in 2014 …………………………...………………………………………….14

Table3 Toxic elements that can be harmful to human health and environment………….……...16

Table4 Advantages and disadvantages various treatment methods………………………….…..19

Table5 Summary of Results of Thiosulphate leaching from various literature reviews…………26

Table6 Comparison of various leaching processes……………………….……………………...27

Table7 Application of Various EPR approaches………………………………………………...29

Table8 E-Waste generation in Indian states ……………………………………………………..34

Table9 Comparison of E-waste management systems in India and Switzerland on Important

Indicators………………………………………………………………………………………....37

Table10 Comparison of E-Waste management rules 2011 and 2016……………………………42

Table11 Weight of various components of mobile phones……………………………………...46

Table12 Amount of chemicals used in preparation of samples………………………………….54

Table13 Parameters used for leaching of gold from mobile PCBs using 0.1 M ammonium
hydroxide (NH4OH) solution………………………………………………………………….....54

Table14 Parameters used for leaching of gold from mobile PCBs using 0.2 M ammonium
hydroxide (NH4OH) solution…………………………………………………………………….55

Table15 Parameters used for leaching of gold from mobile PCBs using 0.3M ammonium
hydroxide (NH4OH) solution…………………………………………………………………….56

Table16 Parameters used for leaching of gold from mobile PCBs varying solid to liquid ratio...57

Table17 Design Parameters for TCLP (USEPA-1311, 1992)………………………………...…58

3
Table18 Elemental composition of mobile PCB from EDS Analysis…………………………...61

Table19 Results for PCB leaching using aqua regia solution for gold and silver elements……..63

Table20 Gold content (w/w %) in mobile PCBs ……………………………………………..…64

Table21 Result for gold dissolution at 0.1 M NH4OH solution……………………………….....64

Table22 Result for gold dissolution at 0.2 M NH4OH solution………………………………….66

Table23 Result for gold leaching at 0.3 M NH4OH solution…………………………………….68

Table24 Result for gold leaching at different solid to liquid ratio……………………………….70

Table25 Result for silver leaching in thiosulphate solution……………………………………...71

Table26 Result for PCB leaching using aqua regia solution for some heavy metals……………73

Table27 Result for PCB leaching using thiosulphate solution for some heavy metals………….74

Table28 TCLP Results…………………………………………………………………………...76

Table29 Summary of Problem in e-waste management system in India and provision for the
same in E-Waste management rules 2011 and 2016………………………………………….....79

4
 LIST OF FIGURES

Figure1 Global E-Waste production from 2010 to 2018………………………………………...15

Figure2 E-waste treatment priority………………………………………………………………19

Figure3 Flowchart showing different processes used in treatment of e-waste ……………….…21

Figure4 Material and financial flows …………………………………………………………....30

Figure5 E-waste trade system in India…………………………………………………………...35

Figure6 Material and Financial Flow…………………………………………………………….39

Figure7 Flowchart showing Responsibilities of various groups…………………………………41

Figure8 Mobile phones and their PCBs………………………………………………………….48

Figure9 Mobile plastic cover, battery and monitor………………………………………………48

Figure10 Manually shredded Printed Circuit Boards of Mobile phones……………………..….49

Figure11 Leaching of mobile PCBs at 200rpm for 8 hours………………………………….….50

Figure12 Image of shredded mobile PCBs after leaching……………………………………….50

Figure13 a) Acid digestion using hot plate and b) Filtration of sample using Wattmann 42 filter
paper……………………………………………………………………………………………...51

Figure14 Flowchart for the processes involved in the preparation of sample for ICP-MS
analysis……………………………………………………………………………………..…….52

Figure15 TCLP rotator…………………………………………………………………………...59

Figure16 SEM images of mobile PCB powder…………………………………………………..60

Figure17 EDS result of mobile PCB………………………………………………………….….61

Figure18 XRD pattern of powdered PCB………………………………………………………..62

5
Figure19 Effect of thiosulphate on leaching of gold for different CuSO4 Concentrations a) 10
mM; b) 20 mM; c) 30 mM at 0.1 M NH4OH………………………………………………….…65

Figure20 Effect of thiosulphate on leaching of gold for different CuSO4 Concentrations a) 10

mM; b) 20 mM; c) 30 mM at 0.2 M NH4OH………………………………………………….....67

Figure21 Effect of thiosulphate on leaching of gold for different CuSO4 Concentrations a) 10

mM; b) 20 mM; c) 30 mM at 0.3 M NH4OH…………………………………………………….69

Figure22 Effect of solid to liquid ratio on leaching of gold at 200 rpm for 8 hours……………..71

Figure23 TCLP sample pH……………………………………………………………………....75

Figure24 TCLP result…………………………………………………………………………....77

Figure25 First Stage of Material & Waste Generation………………………………………..…78

Figure26 Second stage of material& waste production………………………………………….78

Figure27 Role of ULBs…………………………………………………………………………..85

6
 LIST OF ABBREVIATIONS
PCB-Printed Circuit Board

CPCB-Central Pollution Control Board

TCLP Toxicity Characteristic Leaching Procedure

SEM-Scanning Electron Microscope

XRD X-Ray Diffraction

EDS-Energy-Dispersive X-ray Spectroscopy

EPR- Extended Producer Responsibility

PRO-Producer Responsibility Organization

ARF-Advanced Recycling fee

EEE-Electrical and Electronic Equipment

WEEE-Waste Electrical and Electronic Equipment

SME-Small and Medium Enterprise

ICP-MS- Inductively coupled plasma mass spectrometry

7
 ABSTRACT
Electronic Waste (E-Waste) has emerged as one the fastest growing component of solid waste

these days. It contains both hazardous as well as valuable metals such as Au, Ag, Cu, Pb, Hg etc.

Valuable metals in E-Waste, especially Printed Circuit Board of PCs and Mobile phones are

extracted in informal recycling sector using hazardous lixiviants such as nitric acid. The use of

such hazardous leaching substance has very harmful effects on human health and environment.

This work aims at evaluating the effectiveness of less hazardous Ammonium thiosulphate

lixiviant in leaching gold and silver from Mobile PCBs. Aqua Regia leaching was performed to

get reference value for gold and silver. Toxicity of extract solution has also been analyzed for

heavy metals and accordingly extract solution has been classified as hazardous or non hazardous

solution based on Central Pollution Control Board (CPCB) and TCLP limits. Morphology and

phase identification of Mobile PCB powder was conducted through SEM and XRD Analysis

respectively.

The XRD analysis showed the presence of copper and lead in oxide forms while gold was

present in floride form. The SEM/EDX Analysis was in good agreement with XRD result.

Maximum dissolution of gold in thiosulphate solution was found to be 41.51 % and it was found

in a solution having 0.08M thiosulphate, 0.1 M ammonium hydroxide and 20Mm copper

sulphate concentrations. The influence of ammonium hydroxide along with copper sulphate on

leaching gold was also studied. It was found that maximum dissolution of silver in thiosulphate

was very low just 7.65%. Toxicity study of extract solution revealed that lead concentration in

the solution exceeds the maximum limit set by CPCB and TCLP procedure and thus the solution

falls into the category of “hazardous waste”.

8
Another objective of this work is to identify the problems in implementing Extended Producer

Responsibility (EPR) approach in Indian E-Waste Management System and recommend some

measures after studying the successful implementation of EPR in Switzerland. The major

problems associated with India e-waste management were found to be (a) the presence of

powerful informal recycling sector,(b) reluctance of manufacturers to mutualize their

responsibility,(c)Unorganized new electronic goods market(d) low government participation (e)

lack of coordination & information flow between stakeholders. Taking into consideration Indian

social, cultural and economical background, recommendations based on Switzerland EPR

experience have been proposed in chapter5.

9
 CHAPTER-1

INTRODUCTION
1.1. General Introduction

Developments in recent times have undoubtedly enhanced our living standards. Revolution in IT

field has transformed our lifestyle, making our day today life easy and simple. Over the last few

decades consumption of electrical and electronic goods has increased manifolds and so has the

generation of electronic waste. With advancement in technologies and reduction in the prices of

electrical equipments, electrical items are now fast becoming obsolete. Consequently, E-Waste

(electronic waste) has now become one of the fastest growing components in the solid waste

stream. These hazardous wastes have posed a severe threat to human life and environment.

Proper management of E-waste has, therefore, assumed much importance these days.

Electronic waste contains both toxic as well as valuable materials. According to ( Wedmer et al.,

2005), hazardous material in e-waste is just 2.7% while plastic accounts for 30% and base and

rare earth metals account for 60%. According to ( Hageluken and Meskers, 2008), a ton of e-

waste ( mobile phones) contains 140g of Palladium, 340 g of gold, 3.5 kg silver, and 130 kg

copper. Globally 80% indium and 50% of antimony production is for electronic industry. Seeing

the composition of mobile phones we can say that a significant portion of precious and special

metals mined globally is used in the manufacture of electrical and electronic goods.

Environmental consequences are also associated with the production of these rare earth metals.

For example, in the production of one tone of Au, Pd or Pt, 10,000 tones of CO 2 is generated

(Premlatha et al., 2014). Proper recycling of E-Waste will thus not only help in conserving non-

renewable natural resources but it also in minimizing the harmful environmental impact

associated with their production.

10
Cyanide leaching process has long been used for leaching gold from E-waste. Similarly acid

leaching and aqua regia leaching of precious metals from E-waste is very popular in informal E-

waste recycling sector in India. Use of these chemicals has very harmful impacts on human

health and environment. The main motive of recyclers in informal sector is to earn profit and

they are least concerned about the health of workers employed in the informal recycling sector.

With environment awareness gaining ground, alternate leaching chemicals with less harmful

impacts are assuming much attention of researchers these days. Some of the chemicals which

have the potential to replace cyanide and other harsh lixiviants like nitric acid and aqua regia as

leaching substance with less harmful impacts are Ammonium Thiosulphate and Thiourea.

As already mentioned, hazardous material accounts for 2.7 percent in E-Waste. High contents of,

arsenic, cadmium, chromium, copper, lead, mercury, zinc etc. in electronic waste poses risk to

both human health and environment. The condition becomes worse when it comes to developing

countries such as India and China. These countries not just product large quantity of E-Waste

domestically but they are also favorite destination for dumping electronic waste by developed

countries especially the European countries and the US. The lack of proper e-waste management

facilities along with cheap illiterate labor aggravates the situation in developing countries. There

are many review papers which have highlighted the harmful effects of e-waste. (Weidmer et al.,

2005, BH Robinson, 2009, Keshav et al., 2009, Kristen et al., 2013).

Two major problems associated with management of electronic waste in developing countries

like India are: First, low E-Waste collection efficiency and absence of sufficient E-Waste

recycling infrastructure, second, to recycle most of electronic waste in these countries in

informal sector using crude method. For countries like India and China, the need of the hour is to

learn from the vast experiences of developing countries in management of E-waste. Reduce;

11
Reuse and Recycle (3Rs) of Japan, Deposit Refund Scheme of the US and the EPR policy of

Switzerland are some of the E-Waste management programs which have been successful in

dealing with e-waste problems. The Extended Producer Responsibility scheme has the highest

success rate in its implementation and it has been adopted successfully by various countries in

the world such Denmark, Germany, Netherlands, Sweden and Switzerland. The EPR

Responsibility is an approach which rests the responsibility of take back, recycling and disposal

of waste with the producers. (Lindhqvist et al., 2000). There are several reviews on E-Waste

management system in developed European countries. (Sinha et al., 2005, Williams et al., 2006,

Kahhat et al., 2008, E Stern et al., 2008, R Widmer, 2009,). Learning from the huge experiences

of these developed countries and applying these schemes in modified forms taking into

considerations local cultural, social and economic factors will definitely help India in

overcoming E-Waste challenges.

1.2. Definition and Composition of E-waste

Any electrical and electronic equipment or its parts which is no longer useful to its owner comes

under the category of electronic waste. We still do not have universally accepted single

definition for e-waste. The absence of single standard E-Waste definition has resulted in the

disparities in the identification and quantification of waste flows. Thus, this issue needs to be

addressed as early as possible by the global community. However, the most commonly used

definitions of E-Waste along with their references are given in table1.

12
 Table1 Definitions of E-Waste along with their references

Definitions References

“Electrical or electronic equipment which is waste, including all EU WEEE Directive

components, sub-assemblies and consumables, which are part of

the product at the time of discarding.”

“Any appliance using an electric power supply that has reached its The Organization for

end-of-life.” Economic Co-operation and

Development (OECD)

E-waste refers to “The reverse supply chain which collects Solving the E-waste

products no longer desired by a given consumer and refurbishes problem (StEP)

for other consumers, recyclers, or otherwise processes wastes.”

E-Waste composition

E-Waste consists of both hazardous and non-hazardous materials. It generally consists of plastic,

glass, rubber, ferrous and non-ferrous metals, PCBs and other items. Iron and steel accounts for

more than 50% of e-waste, plastic for 21% and non-ferrous metals for 13%. A mobile phone

generally consists of more than 40 elements (United Nations Environment Program, 2009; Izatt

et al., 2012) which includes rare earth metals like gold and silver, base metals like tin and

copper and other important metals like cobalt antimony etc. On an average, a mobile phone

typically contains 77% plastic and 23 % metals. Mobile phones generally consist of

13
approximately 40% metal, 40% plastic by weight, glass/ceramic and other miscellaneous

material. As per (East Caribbean Telecommunications Authority project, 1997), a mobile phone

contains 49% of Copper, 21.8% of Zinc, 11.6 %, Iron, 6.5% Nickel, 5.5% Aluminum, 1.9%Lead,

1.7%Tin, 1.5%Silver, 0.5%Chromium, 0.1% Gold and Palladium in trace amount.

Table2 Quantity of valuable metals and toxic substances (in million tons) present in E-

Waste produced globally in 2014.

Elements/Compounds Weight in million tons (MT)

Iron 16500

Copper 1900

Gold 300 (11% of global gold production)

Lead 2.2

Batteries 0.3

CFCs 4400

Source: United Nations report-'Global E-Waste Monitor 2014', 2014.

Note: Iron, gold, silver, copper, palladium, aluminum etc. worth $ 52 billion was generated in

year 2014 alone.

1.3. Global E-Waste generations

According to the 'Global E-Waste Monitor 2014', published by United Nations University

(UNU), the US and China together produced 32 % of total electronic waste produced globally.

India occupies fifth place globally in production of electronic waste. Asia is the largest producer

of e-waste producing 16Mt of waste. China with 6.0 Mt, Japan with 2.2 Mt and India with 1.7 Mt

are three highest e-waste producing nations in Asia. As per the report E-Waste generation may

14
exceed 50 Mt by 2018. Global E-Waste generation from year 2010 to 2018 is given in the Figure

1.

60
49.8
50 47.8
45.7
43.8
41.8
39.8
40 37.8
35.8
33.8
E-WASTE
(Mt)

30

20

10

0
2010 2011 2012 2013 2014 2015 2016 2017 2018

Year

Figure1 Global E-Waste production from 2010 to 2018

Source: United Nations report-'Global E-Waste Monitor 2014’.

(Note: The data from 2015 onwards are predicted data.)

1.4. Harmful Impacts of E-Waste on Human health

Electronic waste contains toxic and carcinogenic matter such as Arsenic, Lead, Mercury,

Chromium, Brominated Flame Retarders (BFRs), etc. Such toxic substances leach into soil, air,

and water when treated in informal sector or simply dumped in landfills. Thus they have impacts

on human health and environment when managed improperly. For example, mercury is mobile in

nature and bioaccumulative. Mercury permanently impairs central nervous system, lungs and

kidneys. Similarly, Lead exposure can be detrimental to the reproductive and nervous systems.

15
The impact becomes more pronounced in countries like India where a large number of urban

people work in informal e-waste recycling sector without any safety measures.

Table3 Toxic elements that can be harmful to human health and environment

Metal Harmful effects

Lead It has harmful effects on the reproductive system. High quantities can be

fatal. Thwarts mental development of children.

Mercury Methylated mercury is toxic and biocumulative in nature. It severely affects

nervous system, kidney and immune system.

Plastic On burning it releases carcinogenic dioxins and furans. They affect

reproductive and immune systems.

Cadmium It is a carcinogenic substance and its Long term exposure cause severe pain

in joints and spine. It is also known to cause kidney damage.

Acid Lungs problem, eye and skin problem when comes in contact with them.

Chromium damages liver and kidneys and also cause bronchial diseases

Beryllium It is a carcinogenic substance and it causes lung diseases.

1.5. Objectives

Objective1

The main objective of this thesis is to characterize Mobile Printed Circuit Board for gold and

silver using ammonium thiosulphate. The study also focuses on the role of copper sulphate as an

oxidizing agent in dissolution of gold in ammonium-thiosulphate solution. This study also

includes

16
1. Characterization of mobile PCB sample in terms of XRD and SEM before leaching and

thereby better understand the process involved in leaching.

2. Characterization of mobile PCB sample with aqua regia for gold and silver to get an idea

about the leach ability of precious metal using harsh chemical.

Objective2

To analyze toxicity of gold extract solutions of ammonium thiosulphate and aqua regia by

comparing concentrations of heavy metals in these solutions with maximum permissible limits

set by CPCB and Federal TCLP Procedure for listing a substance as hazardous waste. This

objective also includes the study of leach ability of heavy metals from mobile phones in

conditions simulating landfill.

Objective3

To identify the problems associated with implementation of Extended Producer Responsibility

(EPR) strategy in E-Waste Management System in India and recommend some measures based

on the successful implementation of EPR approach in Switzerland E-Waste Management

System. 2. The objective also includes the study of provisions in E-Waste management Rules

India 2016.

Note: Switzerland was chosen for study because it is the first country in the world to have

successfully managed the nuisance posed by electronic waste. Also, e-waste management system

in Switzerland was developed by the initiative of e-waste manufacturer without support of

government in the beginning.

17
 CHAPTER-2

LITERATURE REVIEW

Literature review section has been divided into two sub headings. The first sub heading covers

the literature review of various metal extraction technologies and their advantages and

disadvantages. Thiosulphate leaching has been separately discussed. While under the second

sub-heading E-waste management policies and practices in Switzerland has been discussed.

2.1. Literature review of metal extraction processes.

The main options currently available for e-waste treatment are: 1) Reuse, 2) Remanufacturing/

recycling and 3) Incineration & land filling. The first priority should be given to reuse and

remanufacturing as it enhances the life of electronic waste. Electronic equipment should be sent

for recycling only when it is no longer useful. Recycling process consists of three steps: (a)

disassembly: it involves segregating hazardous and valuable components and it is a very

important part of e-waste recycling; (b) upgrading: It involves upgrading valuable substances

using metallurgical process desirable level. (c) Refining: It is the last step where recovered

materials are purified using chemical processing. (Cui et al., 2003). Another option available for

treatment of e-waste is incineration & land filling. This option should be avoided as far as

possible because 1) there are highly dependent on investment and 2) land filling requires a large

portion of land and it also entails leaching problem and 3) incineration of e waste is dangerous

for environment. For example, copper acts as a catalyst in dioxin formation when brominated

flame-retardants are incinerated.

18
 Figure2 E-waste treatment priorities

Table4 Advantages and disadvantages various treatment methods

REUSE/REMANUFACTURE RECYCLE INCINERATION/LANDFILLING

Advantages Advantages Advantages

1. End of life of equipment 1. Saving in 1. It may offer a feasible option for energy

increases. energy. recovery from e-waste with the installation

2. Reduction in the volume of e- 2. Reduction of a comprehensive emission control

waste. in pollutions. system.

3. No stress on environment and 3. Saves Disadvantages

limited resource. precious 1. Highly depended on investments.

Disadvantage natural 2.Environment pollution

In the name of charity, e- waste is resources. 3. Landfill may pollute underground water.

dumped into developing country.

From the above discussion it is now clear that once the equipment becomes unusable, the priority

should be given to recycling. In the last refining stage of recycling, metal is either melted or

extracted using various leaching processes.

19
2.1.1. Classification of metal extraction processes.

The technology to extract precious metal from electronic waste can be broadly classified into

Pyrometallurgical process, Hydrometallurgical process and Biometallurgical process. (Cui et al.,

2008). For the last few decades Pyrometallurgical process has been used to treat e-waste. It

involves melting process and reactions in a gas phase at high temperatures. However, this

process has several environmental consequences. In the last two decades, most of the research

works have remained focused on the recovery of rare earth metals with the help of

hydrometallurgical process. Compared to the Pyrometallurgical process, this process is exact,

predictable, and easily controlled. Hydrometallurgical extraction process has been briefly

discussed in the sections below.

20
 Figure3 Flowchart showing different processes used in treatment of e-waste

Source: Precious metal recovery from waste printed circuit boards using cyanide and non-
cyanide lixiviants – A review, 2015)

21
2.1.2. Hydrometallurgical processes

Hydrometallurgical metal extraction process broadly involves two steps. In the first step metals

are leached out using various chemicals such as cyanide, aqua regia, thiosulphate etc. while in

the second step recovery of metals from leached out solution is carried out various processes

such as ion –exchange, activated carbon process etc.

Leaching of metals

Leaching is the technique of extraction of soluble content of a solid with the help of a solvent.

The most commonly used leaching agents are cyanide, halides, thiourea and thiosulfate. The use

cyanide, aqua regia, HNO3 as leaching chemical has detrimental effect to environment and

human health. Non cyanide processes such as thiourea and thiosulphate leaching has potential to

replace Cyanide as leaching chemical.

Cyanide leaching process

It is most commonly used lixiviant in the mining industries for removing gold from sulphide

ores. The overall reaction involves

4Au+8CN−→4Au (CN) 2−+4e

O2+2H2O+4e→4OH−

Advantages:

1. The aurocyanide (Au (CN) 2- ) formed in the reaction is quite stable.

2. This process takes place in alkaline environment and it does not require special container for

reaction to take place.

22
3. Dissolution of base metals is substantially reduced which are otherwise produced in acidic

medium.

Limitations

1. A number of environmental accidents at several gold mines have raised concerns over the

use of cyanide as a leaching agent. (Hilson, A.J. Monhemius, 2006).

Halide Leaching

The most commonly used halides are: Fluorine, chlorine, bromine, and iodine. Among these

halides, only chlorine has been applied at an industrial scale. The most traditional medium for

dissolving gold is aqua regia, a mixture of HCl and Nitric acid in the ratio of 3:1. The reactions

are as follows (Zhang et al, 2008):

2HNO3+6HCl→2NO+4H2O+3Cl2

2Au+11HCl+3HNO3→2HAuCl4+3NOCl+6H2O

Limitations:

1. Stainless steel and rubber-lined equipments are required due to high corrosive and oxidizing

conditions

2. Chlorine gas emission is very poisonous.

3. Not ecofriendly.

Advantages:

1. More than 99% extraction of metals using aqua regia.

23
2. less time consuming process.

3. Simple and easy process.

Thiourea leaching ((NH2)2CS) Thiourea and thiosulphate is one of the most economical

substitute of cyanide as a lixiviant. Thiourea is very efficient in dissolving gold in acidic

conditions with gold extraction rate up to 90% (Zhang et al, 2008). Ferric sulfate acts as

oxidizing agent. The anodic reaction is

Au+2CS (NH2)2→Au (CS (NH2)2)2+ +e

Limitations:

1. High consumption of thiourea and ferric sulfate

2. More expensive than cyanide process.

3. More developmental processes are required for gold recovery

2.1.3. Thiosulphate leaching

Chemistry of thiosulphate leaching

Effect of ammonia

Alkaline solution is used to retard the breakdown of thiosulphate at low pH. The role of

ammonia is to prevent the formation of sulphur coating on gold surface and thus dissolve gold

into solution as amine complex. This amine complex reacts with thiosulphate as shown below

Au(NH3)2+ +2S2O32-= Au(S2O3)23- +2NH3

The most important function of ammonia is to stabilize Cu2+ ions in ammonia solution as

discussed below (Abbruzzese et al, 1995).

24
Effect of copper

Gold dissolution is effective in effective with copper as oxidizing agent rather oxygen. Copper

oxidizes metallic gold into Au+ as shown below

Au+5S2O32−+Cu (NH3)42+→Au (S2O3)23−+4NH3+Cu (S2O3)35−

The increase in dissolution of gold in thiosulphate solution is due to the formation copper amine

complex. The leaching solution contains gold as aurouthiosulphate

Literature Review of thiosulphate leaching

Non cyanide leaching processes such as thiourea leaching, thiosulphate leaching etc. are

increasingly becoming more and more popular because they are environment friendly and they

have potential to replace cyanide and aqua regia as leaching agents. There are several studies on

the characterization of electronic waste using thiosulphate leaching process. The main problem

with thiosulphate leaching is that it has low extraction of gold and it cannot be applied for

commercial purpose economically as of now (Chandra et al., 2015). However, it should be noted

here that it has low rate of consumption as compared to cyanide lixiviant and its consumption

can be further lowered by using ethylenediaminetetraacetic acid (EDTA) in leaching solution ( D

Feng et al., 2009). Also, thiosulphate can be more effectively used in leaching of gold from ores

containing carbonate and copper when compared to cyanide leaching (Chandra et al., 2015).

Gold recovery using thiosulphate leaching can be enhanced by using Copper and NH3 in the

leaching solution (Yang et al., 2009). Role of copper is to oxidize gold from Au to Au+ (that is

from 0 to +1 oxidation state while the role of ammonia is to stabilize the Cu +2 in the thiosulphate

solution. Another role played by ammonia is that it prevents formation of sulphide layer on the

gold layer and enhances the leaching of gold. (Ha et al., 2010). There are several studies on

25
leaching gold from electronic waste using thiosulphate as leaching agent. Some of these works

along with their results are given in the table below

Table5 Summary of Results of Thiosulphate leaching from various literature reviews

Waste Type Chemicals used Experiment condition Gold % References

PCB of cell 0.1 M Na2S2O3 At 25-26 0C, pH9.9-10.9, 15% Petter et al.,

phones 0.2 M NH4OH (S/L)-1/20,in 4 hrs 2014

0.015-0.03-0.1 M CuSO4

0.01-0.05-0.1 H2O2

PCB 0.1 M (NH4 )2S2O3 (S/L)-10g/l, pH10-10.5, 78.8% Tripathi et

40 mM CuSO4 Temp--25 0C, rpm-250 al., 2012

PCB 0.5 M (NH4 )2S2O3 (S/L)-80g/l, pH 9, at 40 98% Ficerova et

0
0.3 M CuSO4..5H2O C, in 48 hrs al., 2011

1 M NH3
0
PCB Mobile 72.21mMthiosulphate, At 25-26 C, pH 9.9- >90% Ha et al.,

phone 10mM Cu+2 ion, 0.26 M 10.9, (S/L)-1/20,in 4 hrs 2014

ammonia concentration
0
PCB Mobile 0.1 M (NH4 )2S2O3 At 25-26 C, pH 9.9- 15% Petter et al.,

phone 0.2 M NH4OH 10.9, (S/L)-1/20,in 4 hrs 2014

0.015-0.03-0.1 M CuSO4

0.01-0.05-0.1 H2O2

Mobile 0.12 M (NH4 )2S2O3 pH 10-10.5, at 250C, in 2 98% Ha et al.,

phone 20mM Cu hrs. 2010

0.2 M NH3

26
 Table6 Comparison of various leaching processes

Cyanide Halide Thiosulphate Thiourea

Advantages Advantages Advantages Advantages:

1. Does not require special 1. Cheap and simple 1. Most economical substitute of 1. Less hazardous as compared to

container for reaction to take process. cyanide leaching most of the leachate.

place.
2. Less time consuming 2. More than 99% leaching of 2. It has potential to be used

2. Dissolution of base metals is metals. economically with more research

3. More than 99% metal
substantially reduced. in this field.
extraction 3. Leaches gold efficiently.

2. Cheapest leaching process. Disadvantages:

Disadvantage Disadvantages

4. Very hazardous for Lixiviant consumption is high

1. Rubber-lined 1.High consumption of thiourea
environment. and ferric sulfate during extraction.
equipments are required.
2. More expensive than cyanide No economical method for
2. Chlorine gas is
process.
recovery of gold from thiosulfate
released.
3. Gold recovery requires more
solution exists.
development

27
2.2. E-waste Management in Switzerland

Switzerland is a highly developed country with a mature market for electrical and electronic

equipments. It has successfully managed electrical and electronic equipment waste. E-waste

waste collection and management system in Switzerland came into existence even before a legal

backing was provided by Swiss government. Thus Swiss e-waste management system represents

a case where government involvement is minimal and producers play very significant role. This

works on the principle of producer responsibility organization. So what actually is a PRO? In

1990 a group of manufacturers voluntarily came forward to deal with the nuisance of e-waste.

They created an organization which was o look into matter of electronic waste issue, from its

generation and collection to its proper treatment. Thus, a PRO is a cooperative effort by industry

which makes its members responsible for waste generation. The PROs manages finance,

collection, transportation and control systems to ensure proper e-waste management. Two

important PROs in Switzerland are SENS (Swiss Foundation for Waste Management), SWICO

Recycling Guarantee which handle the largest volume of e-waste. The other two PROs are SLRS

and INOBAT. Another important feature of Switzerland e-waste management system is that it is

EPR based.

Extended Producer Responsibility (EPR)

Extended Producer Responsibility is a concept which assigns the responsibility of take back, and

treatment of waste with manufacturers. (Lindhqvist, 2000).

EPR first relieves government of financial liability e-waste treatment, and second it provides and

second encourages manufacturers for better product design. The four principal goals of EPR, ,

are Source reduction, Waste prevention, better product Design and to promote sustainable

28
development. Various EPR approaches and the countries which have adopted them are tabulated

below:

Table7 Application of Various EPR approaches

EPR approach type Type of tools Examples of applied EPR

Product take back program me Mandatory Packaging, (Germany)

Voluntary Packaging (Netherland, Norway)

Regulatory approaches Minimum product standard EEE, Batteries

Disposal ban EEE in landfills (Switzerland)

Mandatory recycling Packaging (Germany, Sweden )

Voluntary industry practice Voluntary code of practicing Transport packaging (Denmark)

Economic Instruments Advanced Recycling Fee EEE (Switzerland, Sweden)

Fees on disposal EEE (Japan)

Source: Producer responsibility for e-waste management: key issues for consideration–learning
from the Swiss experience, 2009.

2.2.1. Material and financial flows

Material flow

The material flow is circular in nature as shown in figure below. The raw material is first of all

used in the production of new goods, which then passes through consumption stage and finally

after the end of life period, it is recycled back into the production of new product. Consumers

dump their waste at retail outlets, railway stations, or recycling centers designated by the

29
authority concerned. From there, the waste is transported to dismantling centers for segregation

of precious and toxic substances. Finally recyclate is sent to smelter for final material recovery.

Financial flow

Processing of electronic waste in ecofriendly way involves a huge sum of money and sale of

precious metals present in electronic waste does not generate sufficient revenue to finance the

overall processing cost of e-waste management system. Therefore this is filled by a special

provision known as advanced recycling fee (ARF). The producers pay the advanced recycling

fee to SWICO or SENS. ARF is ultimately charged on customers while buying product. The

entire financial shortage of e-waste management system is met by the ARF.

Figure4.Material and financial flows (Sinha et al., 2009)

2.2.2. Lessons from Switzerland E-waste management experience

Understanding of these issues will help policy makers from other countries learn from Swiss
experience and develop EPR based E-Waste management system, while taking into

30
consideration social, political cultural and economic background of the concerned country
(Khetriwal et al., 2009)

a. Starting an E-waste management system

There is always dilemma between Policy makers and producers, over who should take the first
step?

Learnings from the Switzerland experience.

With the introduction of “German Packaging Ordinance” in 1991, the IT producers in

Switzerland realized that sooner or later a similar legislation would come into existence for their
products as well. Few producers, therefore, came forward to mutualize responsibility of
developing a common e-waste management system. This resulted in the formation of SWICO
Recycling Guarantee in 1994. Initially it had only a few members but now it has 329
participants.

From the Swiss system we get to learn that rather than waiting for the government to take
initiative, producer can initiate their own system. The system so developed will be flexible and
economical. ERP based E-Waste management policy can be applied to different geographies
with modifications. Apart from Switzerland, other countries to follow Voluntary PROs are
Belgium, Sweden, Norway and Netherland.

b. Financial stability of the system

The recycling fee can be charged at two points one at the time of buying the product or after the
end of life of the product. Switzerland has the provision of advanced recycling fee .Collection of
fee during sale of new product rather than during returning of waste is better because a customer
is comfortable to pay fee in the beginning. Also, advance collection of fee makes financing more
reliable.

Disadvantage of advanced fee is that it hinders environmental friendly design. Another argument
against its favor is that wrong estimation of future generation of electronic waste may destabilize
the system.

c. Take back system

31
There are two options one collective take back and second individual take back. In collective
take back system products of different brands can be deposited at the same collection point and
in individual take back system specific brand product are deposited at a particular center. The
advantages of collective take back are, first, it is consumer oriented and second, it has better
collection efficiency. Switzerland follows collective take back systems. While, in individual take
back system, consumers have to segregate products according to brands and dispose them off in
brand specific collection points, which is not convenient to consumers and thus system has low
collection efficiency.

However, the proponents of the individual system say that it helps companies to improve their
product designs. In the case of Switzerland, the demerits of individual take back system far
outweigh its merits and therefore Switzerland adopts collective take back system.

d. Ensuring compliance

For smooth functioning of the e-waste management system, compliance of all the stakeholders
such as retailers, consumers, and producers is very important. Let us see how Swiss system
overcome non-compliance problem.

First, there is custom control for the imports of new electrical and electronic equipments.
Second, Provision of access to market only after being PRO members. Third, there is
deployment of external auditors to exercise control on recyclers.

e. Restricting monopoly.

There is always the threat of monopoly in the case of collective PRO system. A powerful
recycler may suppress the smaller ones, thus creating monopoly.. Let us see how Switzerland has
overcome this problem.

Recycler monopoly

In Switzerland the recycling permission is given to the lowest bidder. This prevents large firms
from exercising control over the entire recycling sector

32
 Chapter-3

E-WASTE MANAGEMENT SYSTEM IN INDIA

3.1. Existing E-Waste generation and management scenario in India

The hazardous nature of electronic waste has compelled many nations to adopt environmentally

sound management practices to deal with E-Waste, with an aim to control the ever growing

effect of e-waste on human health and environment. For the last three decades electronic waste

management has been the top priority for developed countries while for countries like India

simply replicating the waste management practices of developed countries will not work because

social, cultural and economic conditions in India is different from those in developed countries.

However, a modified version may work in Indian scenario. Before moving into the proposed e-

waste management system, let’s see how e-waste is produced in India. According to (Sushant et

al., 2010), e- waste is generated at three levels.

At the first level, new electrical and electronic equipments enter into India. There is no

generation of e-waste in this stage. In the second stage, EEE passes through consumption stage.

This stage is marked by generation of e-waste. The final stage consists of pre-reprocessing and

reprocessing stage. In the re-processing stage, collection of e-waste is carried out by unorganized

sector with the help of kawadiwala. In the reprocessing stage, e-waste is dismantled and recycled

to recover valuable items.

As per central pollution control board (CPCB) report 2014-2015, India produced 51.4 million

tons of solid waste of which 91% was collected and 27% was treated and remaining 73% was

disposed off at dumping sites. 72 lakh tons of industrial waste, 5.5 lakh tons of plastic, 4.8 lakh

33
tons of medical waste, 18.5 lakh tons of electronic waste are produced annually in India. The e-

waste generation by individual households is relatively low (15) and the rest contributed by

manufacturers. Generation of electronic waste by Indian states is tabulated below.

Table8. E-waste generation in Indian states

State/UT E-waste (tones) State/UT E-waste (tones)

Andaman and Nicobar 92.2 Lakshadweep 7.4

Andhra Pradesh 12780.3 Madhya Pradesh 7800.6

Arunachal Pradesh 131.7 Maharashtra 20270.6

Bihar 2176.7 Manipur 231.7

Assam 3055.6 Meghalaya 211.6

Chandigarh 359.7 Mizoram 79.3

Chhattisgarh 2149.9 Nagaland 145.1

Dadra Nagar Haveli 29.4 Orissa 2937.8

Daman and Diu 40.8 Pondicherry 284.2

Delhi 9729.2 Punjab 6958.5

Goa 427.4 Rajasthan 6326.9

Gujarat 8994.3 Sikkim 78.1

Haryana 4506.9 Tamil Nadu 13486.2

Himachal Pradesh 1595.1 Tripura 378.3

Jammu and Kashmir 1521.5 Uttar Pradesh 10381.1

Jharkhand 2021.6 Uttrakhand 1641.1

Karnataka 9118.7 West Bengal 10059.4

Kerala 6171.8

34
Source: Rajya Sabha E-Waste report 2012

3.1.1. E-waste trade in India

India’s E-waste management system is ill defined and unorganized. The Fig presents overview of
material and money flows of EEE in India.

Figure5 E-waste trade system in India

Source: (A roadmap for development of sustainable e-waste management system in India,
Science of the total environment, 2010).

3.2. Comparison of the two waste management systems

E-Waste recycling industry is India is relatively new one. India already had well established

scrap metal industry which used to extract iron, copper, aluminum etc. When new kind of waste

that is electronic waste became prominent in 1990s, this industry absorbed then because of

35
availability of rare earth metals in them. Given low level of initial investment, several

entrepreneurs have joined the industry. The entire industry is based on the symbiotic relationship

between collectors, dismantlers and recyclers.

Unlike Switzerland, the collection and recycling facilities in India is underdeveloped. Another

important thing that should be noted is that in Switzerland consumers have to pay recycling fee

while in India consumer get money when they sell e-waste to kawadiwala. Kawadiwala in turn

sell these items to trader, recyclers and dismantlers in the informal sectors who finally extract

precious metals just for financial gains without paying much attention to human health and

environment. The two systems can be broadly compared on four parameters (Phillip-et al.,

2005). First comparison is on the basis of electronic waste generation per capita. Switzerland has

higher e-waste per capita as compared to India but when it comes to total generation of e-waste

India far exceeds Switzerland. Second comparison is based on the employment potential. Indian

system has potential to generate more jobs than the Swiss system. In India sorting, dismantling

and recycling operations are carried out manually where the Swiss system is mechanized one.

Third, People employed in e-waste recycling system are semi-skilled and unaware of the harmful

impact associated with e-waste when compared to workers employed in the Swiss system and

finally the Swiss system follows high safety and emission standards while in India though there

are guidelines but there is lack of enforcement. Thus the release of toxics in the environment

during the treatment of waste is high in India.

36
 Table9 Comparison of E-waste management systems in India and Switzerland on

Important Indicators

Indicator Switzerland India

Party involvement

Producer High Low

Consumer High Medium

Retailer High Medium

Collector High High

Government Medium Low

Material flow and control

Per capita generation High Low

Control High Low

Employment Generation Low High

Labour cost High Low

Demand for secondary raw Medium High

material

3.3. Proposed Indian Electronic-waste management system

Several studies on the e-waste management system have found that majority of nations have

favored extended producer responsibility (EPR) for the take back of EEE waste because it is

economically self sustaining. EPR also aims at i) less e-waste generation ii) reduction in

hazardous components of the waste iii) reduction in the use of virgin material; iv) pollution

37
reduction in production stage and v) encouragement of environment friendly design. The

proposed e-waste system, therefore, should follow the EPR mechanism

3.3.1. Material and financial flow

Recycling industries receive material from both consumers as well as manufactures. However,

material flow from consumer ids relatively low. Individual collectors collect waste from

households as well business places by making payment. The price is charged arbitrarily,

depending on collector’s profit margin. Collectors in turn sell their waste to recyclers in informal

sector. Thus material flow is both uncontrolled and unorganized. At no point there is control over

quality and quantity of material flow

Financial flow

In Switzerland recycling is a non-market activity whereas in India it is a market activity carried

out mainly with the motive of economic benefit. Thus recycling is an attractive business in India.

Thus recycling and collection is self reliant in India. Low labor cost along with small initial

investment cost makes it possible for the E-Waste Management system to be self financing. In

case the need for external financing arises. ARF facility akin to the Indian Government Provident

Fund Scheme may be put in place for financial reliability of the system (Sushant et al., 2010). To

discourage the use of hazardous material in electronic goods, tax benefit option may be explored

for the manufactures that are coming up with ecofriendly products or decreasing the use of

hazardous material in their product.

38
 Figure6 Materials and Financial Flow

Source: Producer responsibility for e-waste management: key issues for consideration–learning

from the Swiss experience. (Sinha et al., 2009).

3.3.2. Responsibility of various actors

For any waste management system to work efficiently, there must be high level of interaction

between various players such as government, producers, consumers, collectors and recyclers.

They have to fulfill their financial, informational, physical and legal responsibilities to ensure

proper working of the management system. One of the main reasons why Switzerland has been

successful in managing e-waste is that it has high degree of interactions between concerned

parties whereas India lacks the same. According to Lindhqvist, 2000, there should be strong

feedback mechanism between producers, users and authority. Thus stakeholder consultation

forms an integral part of EPR process.

39
Role of the government

Government has to play a very proactive role for the successful implementation of e-waste

management system. It has to not only legal policy framework for EPR but also create awareness

about this. Though government does not take part in day to day activity in e-waste management

(as in Switzerland), it has to coordinate and monitor the functioning of the system. Apart from

these, the following should be initiated for setting the E-waste management system for India:

1. A detailed and effective rules and regulations on collection handling, dismantling and

recycling of WEEE should be in place.

2. A uniform National E-waste policy for E-waste management should be devised out.

3. A set of guidelines and standard for the certification for the recycling and disposal companies

be created to ensure environmentally sound processing of WEEE.

4. Come with proper infrastructure facilities and support system to reduce compliance cost.

5. Bring as many SMEs as possible within formal e-waste management system by supporting

them with training, testing, designing facilities. This can also be done through training

institutions, academia and facilitating Public–Private–Partnership.

6. Encourage research on the development of environment friendly design, developing methods

for reducing compliance cost especially for SMEs.

40
 Technical & certification group
 Preparing certification guidelines for e-waste recycling
 Evaluating EIA for e-waste recycling
 Controlling, monitoring and evaluating recycling facilities
 Calculating ARF for various stakeholders
 Coordinating various groups for better implementation of e waste management system

Finance group Coordinator/Manager Legal groups

 Managing financial  Design implementation  Ensuring legal

details of the of e-waste system compliance.
system.  Maintain coordination  Issuing legal notice
 Finalizing ARF by b/n government, to non-complying
consultation with regulatory bodies and members.
various groups. NGOs  Play the role a legal
 Preparing guidelines  Maintain coordination advisor in case of
for benefits of between internal implementation of
various stakeholders groups and external e-waste
 Work in consulting bodies management
coordination with system.
different groups

Communication and information group

 Maintaining database for the recycling system.

 Promoting the creation of new recycling facilities.
 Providing guidance in case of setting up new e-waste management system.
 Creating awareness of rules and regulations among various stakeholders such as recyclers, dismantler
etc.
 Work in coordination with various stakeholders.
3.4 Comparison of E-Waste management rules 2011 and 2016

Figure 7 Flowchart showing Responsibilities of various groups

41
For any waste management practice to work properly in a country, there must be legal backing in

the form of rules and regulation. These rules and regulations ensure compliance by clearly

defining responsibilities various players involved in e-waste management system. From time to

time, India also has come up with several waste management rules. Let’s have a brief look on

Comparison of E-Waste management rules 2011 and 2016

Table10 Comparison of E-Waste management rules 2011 and 2016

E-Waste E-Waste management Reasons /Implications

management Rules, rules,2016

2011

1.Applicability

Producer, consumer, Extended to manufacturer, dealer, To address leakage of e-waste to

recycler, collection refurbisher, and Producer informal sector at all stages.

centre and dismantler Responsibility Organization

2.Exception

Micro and small Micro industries Exemption continues for micro

industries industries.

It must be noted here that small

industries still don’t come under

EPR. But they have to fulfill

manufacture responsibility.

3.Extended producer responsibility

To obtain EPR Single EPR Authorization for Separate EPR authorization leads to

authorization from Producers. CPCB to ensure pan delays

42
both SPCB and PCCs India implementation

for producers and

recyclers

4.Target under EPR approach

No such provision Target based approach for e- Target based approach has been

waste collection with 30% adopted based on experiences of

collection rate in first two years international best practices which

and 70 % by the end of seven indicate higher success rate for

years. implementation of EPR in those

countries having target based EPR

mechanism.

5.Economic instrument for the implementation of the rules

No such provision Deposit Refund Scheme has been This option may facilitate effective

introduced. Extra fee will be implementation of EPR

charged during the sale of new

product and during the return of

product after its end of life money

will be returned with interest.

6.Responsibility of manufacturer

No such provision Manufacturers are responsible for To divert flow of waste from

the collection of waste generated informal to formal recyclers.

during manufacturing process and

sent it licensed recyclers

43
7.Responsibility of Bulk consumer

Bulk consumer means Addition of health care facility To put obligations on bulk

EEE users in centers under bulk consumers. consumers

government

departments, banks,

educational

institutions etc.

8.Responsibility of state government

No provision 1. Department of industry in state For effective implementation

is responsible for allocating space

for recycling and dismantling

facility.

2. Department of labor in state is

responsible for ensure safety to

workers employed in recycling

sector.

3. Government to prepare plan

for effective implementation of

the pregame and summit the

report to environment ministry

annually.

44
 CHAPTER 4

METHODOLOGY

As it has been already mentioned, mobile phones contain just 2.7 % of toxic substances whereas

precious metals such as copper, gold, silver, palladium, zinc, etc. account for more than 40% of

mobile PCBs. Chemicals such as cyanide, aqua regia, nitric acid, etc. have long been used to

extract precious metals from e-waste. These chemicals are, however, hazardous and thus pose

risk to risk to both human health and environment. Less toxic chemicals such as thiosulphate and

thiourea have potential to replace them as leaching chemicals without causing much damage to

environment and thus have assumed much importance these days.

In this study the effectiveness of ammonium thiosulphate in leaching gold from mobile PCBs has

been studied by varying its concentration from 0.04M to 0.16M in NH4OH solution. The effect

of copper sulphate (as oxidizing agent) in gold extraction has also been analyzed. Copper

sulphate concentrations of 10mM, 20mM and 30mM have been in thiosulphate solution to

analyze the role of copper sulphate as oxidizing agent. Study of Toxicity characteristics of spent

liquor of aqua regia and thiosulphate solutions have also been carried out to determine their

hazardous characteristics. TCLP test has been performed on mobile PCBs to determine the

release of toxic metals lead, mercury, arsenic etc. into the environment simulating landfill

conditions.

45
4.1. Material and Methods

4.1.1. Collection of mobile phones

Obsolete Mobile phones were collected from different sources and then they were manually

disassembled to separate plastic cover, PCBs, batteries and monitor. The weight of each of the

component of mobile phone was noted down and tabulated in table11. It should be noted here

that mobile phones were of different companies.

Table11 Weight of various components of mobile phones

Mobile set Mobile weight with Mobile weight without Plastic PCBs

battery (g) battery (g) content weight

(g) (g)

LG-Wireless 82.14 53.53 33.24 20.26

Micromax - 79.24 42.21 31.92

Karbonn 84.13 58.51 28.80 21.11

Spice 80.03 42.38 30.32 10.11

Kechaoda - 75.12 44.92 22.74

Opal 139.24 107.26 62.50 13.22

Bluetooth - 51.42 23.96 18.88

Monix - 77.02 58.30 14.16

Nokia 89.63 68.35 - 31.23

Samsung 100.50 76.04 23.53 21.26

Nokia 62.74 41.80 20.42 15.26

46
Fannaod - 61.47 24.39 19.15

Spice M-5500 - 42.65 23.90 18.37

Blackberry - 72.83 40.14 21.24

Micromax 101.99 85.10 35.26 34.26

Nokia 1600 80.60 53.21 40.12 10.21

Samsung 83.20 60.14 45.13 12.42

Spice 103.86 78.19 42.16 20.12

Micromax 65.11 40.23 19.34 12.23

Nokia 73.23 40.42 23.15 10.20

47
 Figure8 Mobile phones and their PCBs

Figure9 Mobile plastic cover, battery and monitor

48
4.1.2. Shredding of PCBs

For leaching, either complete printed circuit board or shredded PCBs can be used. For this study

mobile PCBs have been shredded manually into 3mm*3mm (approximate) size particles. It

should be noted here that the size of the particle may not uniform as the shredding was done

manually using scissor.

Figure10Manually shredded Printed Circuit Boards of Mobile phones.

4.1.3. Leaching of mobile PCBs

Characterization of two mobile PCB samples were carried out using aqua regia lixiviant to get

some idea about leaching potential of some harsh leaching chemicals. Rest of the mobile

samples were characterized using alternate leaching chemical ammonium thiosulphate in shaker

machine at 200 rpm, room temperature, for contact time period of 8 hours. Leaching Process

and preparation of samples for leaching using aqua regia and thiosulphate lixiviants have been

discussed in detail in section 4.2 below.

49
 Figure11 Leaching of mobile PCBs at 200rpm for 8 hours

Figure12 Image of shredded mobile PCBs after leaching

4.1.4. Acid digestion of mobile PCBs.

A 100 mL well mixed sample was taken in griffin beaker and 3 mL of concentrated nitric acid

was added to it. The beaker was then covered with a ribbed glass and placed on hot plate. The

solution was heated till its volume reduced to 5 mL The solution was then cooled and another 3

mL of concentrated HNO3 was added to it. The beaker was now covered with non-ribbed watch

glass and placed on hot plate. The solution was heated with additional acid was necessary till the

50
digestion was complete. The beaker was now uncovered and the solution was evaporated to 3

mL volume. The beaker was cooled and 10 ml of HCl (1:1) was to 100 mL of the final solution.

The beaker was now covered and the solution was refluxed for another 15 minutes. The solution

was finally filtered using Wattmann 42 filter paper and adjusted to final volume of 100 mL. The

sample was now ready for ICP-MS analysis.

Figure13 a) Acid digestion using hot plate and b) Filtration of sample using Wattmann 42

filter paper

All the steps involved in the study have been shown in the flowchart given below. The PCBs

were first characterized using aqua regia solution and then with thiosulphate solution. Finally the

leached solution was analyzed using ICP-MS.

51
Figure14 Flowchart for the processes involved in the preparation of sample for ICP-MS

analysis.

52
4.1.5. SEM-EDS Analysis

The SEM-EDS analysis was done to mobile pcbs sample to know the surface texture and

imaging of particles present in it, it gives the surface texture information in form of elemental

composition. A prior sample preparation is required in form of attaching the sample to the carbon

tape and surface gold coating is done.

4.1.6. XRD-Analysis

It is a technique to identify crystalline mineral compounds present in the sample. The humps or

broad patterns nevertheless shown in XRD infer the presence of crystalline minerals and peaks in

the graphs indicates the crystalline minerals (Ward & French, 2005). It is a very important

characterization technique.

4.2. Leaching of Mobile PCBs using Aqua Regia and Ammonium Thiosulphate

Leaching of mobile PCBs using aqua regia (A mix of nitric acid and hydrochloric acid in

the molar ratio of 1:3) to get reference values for gold and silver along with other heavy

metals present in the PCBs.

Sample Preparation

a. 4 g mobile PCB granules was taken for 100 ml of aqua regia solution.

b. First of all, chemical coating from PCB granules was removed using10 M NaOH by dipping

PCB into it for 10 hrs.

c. The granules were then cleaned with distilled water to eliminate the presence of NaOH and

finally PCB was treated with aqua regia to extract metals.

d. The leached out solution was then digested using acid and finally analyzed with the help of

ICP-MS for PCB characterization.

53
Leaching of mobile PCBs for gold and silver using ammonium thiosulphate, CuSo4.5H2O,

and NH4OH.

Sample preparation

 36 number of Samples were prepared

 4 g of shredded PCBs were used for 100 ml of solution

 Mobile PCBs was leached at 200 RPM for 8 hrs.

 Solution pH was maintained at 10-10.5 using sodium hydroxide.

Table12 Amount of chemicals used in preparation of samples

Ammonium thiosulphate 0.04 M (0.6 g) &0.08 M 0.12 M 0.16 M

(1.2 g) (1.8g) (2.4g)

NH4 OH 0.1 M 0.2M 0.3M

3.75 ml 7.5 ml 11.25 ml

Copper Sulphate 10 mM 20 mM 30 mM

1.25 2.5 3.25

Step 1

Table13 Parameters used for leaching of gold from mobile PCBs using 0.1 M ammonium

hydroxide (NH4OH) solution

Sample [S2O3]-2 (M) [NH4OH] (M) [Cu+2] (mM) Time (hrs) pH Ratio (S/L)

54
 1. 0.04 0.1 10 8 10.1 1/25

2. 0.04 0.1 20 8 10.3 1/25

3. 0.04 0.1 30 8 10.2 1/25

4. 0.08 0.1 10 8 10.2 1/25

5. 0.08 0.1 20 8 10.1 1/25

6. 0.08 0.1 30 8 10.3 1/25

7. 0.12 0.1 10 8 10.2 1/25

8. 0.12 0.1 20 8 10 1/25

9. 0.12 0.1 30 8 10.4 1/25

10. 0.16 0.1 10 8 10.3 1/25

11. 0.16 0.1 20 8 10.1 1/25

12. 0.16 0.1 30 8 10.4 1/25

Step 2

Table14 Parameters used for leaching of gold from mobile PCBs using 0.2 M ammonium

hydroxide (NH4OH) solution

Sample [S2O3]-2 (M) [NH4OH] (M) [Cu+2] (mM) Time (hrs) pH Ratio (S/L)

1. 0.04 0.2 10 8 10.0 1/25

2. 0.04 0.2 20 8 10.3 1/25

3. 0.04 0.2 30 8 10.2 1/25

4. 0.08 0.2 10 8 10.2 1/25

5. 0.08 0.2 20 8 10.1 1/25

6. 0.08 0.2 30 8 10.3 1/25

55
 7. 0.12 0.2 10 8 10.2 1/25

8. 0.12 0.2 20 8 10 1/25

9. 0.12 0.2 30 8 10.4 1/25

10. 0.16 0.2 10 8 10.3 1/25

11. 0.16 0.2 20 8 10.1 1/25

12. 0.16 0.2 30 8 10.4 1/25

Step 3

Table15 Parameters used for leaching of gold from mobile PCBs using 0.3M ammonium

hydroxide (NH4OH) solution

Sample [S2O3]-2 (M) [NH4OH] (M) [Cu+2] (mM) Time (hrs) pH Ratio (S/L)

1. 0.04 0.3 10 8 10.1 1/25

2. 0.04 0.3 20 8 10.0 1/25

3. 0.04 0.3 30 8 10.1 1/25

4. 0.08 0.3 10 8 10.2 1/25

5. 0.08 0.3 20 8 10.1 1/25

6. 0.08 0.3 30 8 10.3 1/25

7. 0.12 0.3 10 8 10.2 1/25

8. 0.12 0.3 20 8 10 1/25

9. 0.12 0.3 30 8 10.4 1/25

10. 0.16 0.3 10 8 10.3 1/25

56
 11. 0.16 0.3 20 8 10.1 1/25

12. 0.16 0.3 30 8 10.4 1/25

Preparing and analyzing mobile leached solutions having solid to liquid ratio as 10 g/l,

20g/l, 30g/l, 40g/l and 50g/l to determine the solid liquid ratio for maximum leaching of

gold.

Sample preparation

 Preparing solutions of (S/L) ratio of 1/100, 1/50, 3/100, 1/25 and 1/20.

 RPM-200

 pH10-10.5

Table16 Parameters used for leaching of gold from mobile PCBs varying solid to liquid
ratio.

Sample [S2O3]-2 (M) [NH4OH] (M) [Cu+2] (mM) Time (hrs) pH Ratio (S/L)

1. 0.12 0.2 20 8 10.2 1100

2. 0.12 0.2 20 8 10.1 1/50

3. 0.12 0.2 20 8 10.3 3/100

4. 0.12 0.2 20 8 10.2 1/25

5. 0.12 0.2 20 8 10 1/20

57
4.3. TCLP Test for Mobile PCB

To conduct TCLP (Batch Extraction test) to access the leaching potential of different heavy

metals present in Printed Circuit Board to evaluate risk associated with disposal of

leaching solution to water bodies.

TCLP- Toxicity characteristic leaching procedure

This test is basic and most widely used batch test defined by RCRA to characterize the waste as

hazardous or not. It involves particle size reduced mass is kept contact with the specific fluid for

a fixed time and then leachate is extracted by filtering the sample, the following parameters are

the guidelines for using TCLP.

Table17 Design Parameters for TCLP (USEPA-1311, 1992)

Parameters TCLP

L/S Ratio 20:1

Ph Normal waste =4.93±0.05

For high alkaline waste = 2.88±0.05

Extracting fluid Normal waste =Acetic acid + NaOH

For high alkaline waste = Acetic acid

Time and RPM 18 hours @ 30±2 rpm

maintained

58
 Applicability Simulate material sitting in a landfill for a number of years, to determine

whether a solid waste is a toxicity characteristic hazardous waste

Figure15 TCLP rotator

For the sample of mobile PCBs, Acetic Acid +NaOH is used as extracting fluid with 128.6 mL

of 1N sodium hydroxide (NaOH) and 11.4 ml of acetic acid is diluted to 2 liters to make a pH of

4.93±0.05. A 10 gm of the sample is taken and 200 ml of prepared fluid is added to maintain L/S

ratio of 20:1, similarly duplicate and triplicate was prepared. This was kept in TCLP shaker,

rotated for 18 hours @ 30+2 rpm and then filtered through the 0.8 μ and few drops of nitric acid

is added to get pH below 2 for preservation of sample and sample is analyzed further

59
 CHAPTER 5

RESULT AND DISCUSSION

5.1. Scanning Electron Microscopic Analysis (SEM)

To study the morphology of powdered printed circuit board of mobile phones SEM analysis was

carried out. PCB SEM image shows fibrous structure as shown in fig. (a). This fiber structures

are fiberglass which acts as reinforce material in PCB.(Liu et al, 2009). These fiber structures are

long and combined through bonding action of resins. (Guo et al, 2010). Epoxy resin coating on

fibrous structures has been shown in fig. (b).Certain amount of base and precious material get

pulverized during crushing and in the SEM image I could not identify base and precious metals.

However, Energy Dispersive X-Ray (EDX) analysis of the same image revealed the presence

base and precious metals as shown in table

(a) (b)

Figure16 SEM images of mobile PCB powder

60
 Figure17 EDS result of mobile PCB

Table18 Elemental composition of mobile PCB from EDS Analysis

Element Weight% Atomic%

Cu K 11.89 28.26

Ag L 8.42 11.78

Pt M 13.98 10.82

Au M 10.62 8.14

Hg M 35.64 26.83

Pb M 19.45 14.17

Totals 100.00

61
5.2. X-ray Diffraction Analysis (XRD)

Phase identification of Mobile Printed Circuit Board was carried out by XRD Analysis. The

analysis revealed the presence of Lead and copper in the oxide form while the gold was found in

floride form. The presence of silver was also indicated in the analysis. The result of XRD

Analysis is in good agreement with SEM Analysis and ICP-MS Analysis.

Figure18 XRD pattern of powdered PCB

5.3. Characterization of Mobile PCBs for Gold and silver

Aqua Regia Leaching

5.3.1. Characterization of gold and silver elements in mobile PCBs using aqua regia (A mix

of nitric acid and hydrochloric acid in the molar ratio of 1:3).

62
 Table19 Results for PCB leaching using aqua regia solution for gold and silver elements.

Elements Total Concentration in Concentration of elements % of metal

ppm ( as per literature) leached in aqua regia solution extracted

(ppm)

Gold 8.4 6.11 72.68%

Silver 20 6.23 31.15%

On converting concentrations (ppm) of gold and silver in gram/ ton of PCB, we get to know that

152.5 g of gold and 155.75 g of silver can be extracted from 1 ton of PCBs using aqua regia. We

can notice from the table that gold dissolution was 72.68% in aqua regia solution while silver

dissolution was just 7.63%. Thus we can say that aqua regia was not effective in leaching silver

from mobile PCBs. The result of silver dissolution is higher than the result of Petter et al. (2014)

which is 8% for silver. The reason for low dissolution of silver in aqua regia is the formation of

insoluble compound of AgCl in the solution.(Petter et al.,2014)

Ammonium Thiosulphate Leaching

5.3.2. Characterization of gold and silver elements from mobile PCBS using ammonium

thiosulphate, CuSO4 .5H2O andNH4OH

All the results are expressed as % of the total amount of gold present in the PCBs. There are

several reviews on the total amount of gold present (expressed as weight % of PCB) in the

printed circuit board as give in the table below. For this study 0.021% of the weight of PCB has

been taken as the total amount of gold present in PCB.(Tripathi et al., 2012).

63
 Table20 Gold content (w/w %) in mobile PCBs

Researchers Park and Tripathi et al., Tuncuk et al., Sum et al., Guo et al.,

Fray, 2009 2012 2012 2005 2009

Wt % Gold 0.025 0.021 0.035 0.1 0.008

Expressing result in %

Total amount of gold present in 4 g of PCB= (0.021/100)*4=0.00084g

4 g of PCB was taken for 100 ml of solution.

Therefore, total concentration of gold in solution in ppm = (0.00084)/100*10^6 = 8.4 ppm

% of gold leached in the solution using thiosulphate as leaching chemical = (Concentration of

gold leached in solution)/8.4*100

Leaching mobile PCBs using 0.1 molar ammonium hydroxide (NH4OH) solution

Table21 Result for gold dissolution at 0.1 M NH4OH solution.

Sample [S2O3]-2 [NH4OH] [Cu+2] Concentration of Au leached % of gold

(M) (M) (mM) in thiosulphate solution leached in the

(ppm) solution

1 0.04 0.1 10 1.10 13.20

2. 0.08 0.1 10 2.14 25.44

3. 0.12 0.1 10 2.09 24.86

4. 0.16 0.1 10 2.08 24.76

64
 5 0.04 0.1 20 1.26 15.01

6. 0.08 0.1 20 3.49 41.51

7. 0.12 0.1 20 2.40 28.50

8. 0.16 0.1 20 1.21 14.43

9. 0.04 0.1 30 2.06 24.50

10. 0.08 0.1 30 2.11 25.07

11. 0.12 0.1 30 0.01 0.02

12. 0.16 0.1 30 <M DL <MDL

0.1 M NH4OH
45

40

35
Copper
30
sulphate
Gold %

25
10 mM
20
20 mM
15 30 mM
10

0
0 0.05 0.1 0.15 0.2
-5
Thiosulphate (M)

Figure19: Effect of thiosulphate on leaching of gold for different CuSO4 Concentrations a)

10 mM; b) 20 mM; c) 30 mM at 0.1 M NH4OH.

65
For 0.1 M NH4OH solution, maximum dissolution of gold is 41.51% at 0.08 M thiosulphate and

20 mM copper sulphate concentrations. The figure shows that dissolution of gold increases with

increase in ammonium thiosulphate concentration until 0.08 M, thereafter gold dissolution rate

decreases with increase in thiosulphate concentration. Furthermore, gold dissolution rate is

higher for 20mM copper sulphate solution as compared to 10 mM and 20 mM copper sulphate

solutions. At low thiosulphate concentration dissolution of copper instead of gold takes place

while at high thiosulphate concentration degradation products such as trithionate or tetrathionate

are generated (Hung Ha et al., 2009). The decrease in dissolution of gold at high copper

concentration is due to degradation of thiosulphate to tetrathionate as per reaction shown below

(Aylmore et al., 2000)

2Cu (NH3)42+ + 8S2O32- = 2Cu (S2O3)35- + 8NH3 + S4O62-

Leaching mobile PCBs using 0.2 molar ammonium hydroxide (NH4OH) solution

Table22 Result for gold dissolution at 0.2 M NH4OH solution

Sample [S2O3]-2 [NH4OH] [Cu+2] Concentration of Au leached % of gold

(M) (M) (mM) in thiosulphate solution leached in the

(ppm) solution

1. 0.04 0.2 10 0.69 8.26

2. 0.08 0.2 10 1.40 16.67

3. 0.12 0.2 10 1.20 23.70

4. 0.16 0.2 10 1.52 18.06

5. 0.04 0.2 20 0.64 7.64

66
 6. 0.08 0.2 20 1.23 14.60

7. 0.12 0.2 20 1.20 23.80

8. 0.16 0.2 20 0.63 7.46

9. 0.4 0.2 30 1.20 14.28

10. 0.08 0.2 30 1.73 20.60

11. 0.12 0.2 30 0.63 7.51

12. 0.16 0.2 30 0.60 7.21

0.2 M NH4OH
25

20

15
Gold %

10 mM

10 20 mM
30 mM

0
0 0.05 0.1 0.15 0.2
Thiosulphate (M)

Figure20: Effect of thiosulphate on leaching of gold for different CuSO4 Concentrations a)

10 mM; b) 20 mM; c) 30 mM at 0.2 M NH4OH.

From the above figure, it is clear that dissolution of gold in 0.2 M NH4OH solutions is lower than

that in 0.1 M NH4OH solutions. Also we can notice from the figure that maximum dissolution of

67
gold is at higher thiosulphate concentration (0.12M) for 0.2 M NH4OH solution, while it is at

0.08 M thiosulphate concentration for 0.1 M NH4OH solution. Just in the case of 0.1 M NH4OH

solution, for 0.2 M NH4OH solution also the maximum dissolution of gold is for 20 mM copper

sulphate solution as compared to 10 mM and 30 mM copper sulphate solutions. The probable

reasons for such behavior could be: a) At high ammonia concentrations, solid copper entities

such as oxides of copper (CuO, Cu2O), (NH4)5Cu (S2O3)3 are formed and they hinder the

dissolution of gold by forming coating on gold surface.(Hung Ha et al., 2010). b) Ammonia

stabilizes Cu2+ ions in thiosulphate system thus its presence is important for effective dissolution

of gold (Aylmore et al., 2000). Gold leaching is found to be maximum at 20 mM copper sulphate

concentration as compared to 10 mM and 30mM copper sulphate solutions because at low

copper concentration, limited copper-amine complexes are formed while at higher copper

sulphate concentrations formation of tetrathionate species hinder gold dissolution (Aylmore et

al., 2000).

Leaching mobile PCBs using 0.3 molar ammonium hydroxide (NH4OH) solution

Table23 Result for gold leaching at 0.3 M NH4OH solution

Sample [S2O3]-2 [NH4OH] [Cu+2] Concentration of Au leached % of gold

(M) (M) (mM) in thiosulphate solution leached in the

(ppm) solution

1. 0.04 0.3 10 1.13 13.42

2. 0.08 0.3 10 2.36 28.14

3. 0.12 0.3 10 0.90 10.66

4. 0.16 0.3 10 0.73 8.68

68
 5. 0.04 0.3 20 0.73 8.72

6. 0.08 0.3 20 1.10 13.05

7. 0.12 0.3 20 0.91 10.80

8. 0.16 0.3 20 0.47 5.65

9. 0.04 0.3 30 1.81 21.62

10. 0.08 0.3 30 2.88 34.32

11. 0.12 0.3 30 0.50 5.91

12. 0.16 0.3 30 0.58 6.70

0.3 M NH4OH
40

35

30

25
Gold %

20 10 mM
20 mM
15
30 mM
10

0
0 0.05 0.1 0.15 0.2
Thiosulphate (M)

Figure21 Effect of thiosulphate on leaching of gold for different CuSO4 Concentrations a)

10 mM; b) 20 mM; c) 30 mM at 0.3 M NH4OH.

69
From the figure we can again see that gold dissolution has increased with increase in

thiosulphate concentration and maximum leaching is around 0.08 M thiosulphate concentration.

For 0.3 M NH4OH solution, leaching rate is higher for 30mM copper sulphate solution instead of

20mM copper sulphate solution. The most probable reason for such a behavior could be the

formation of stable copper-amine complex.

Effect of solid to liquid ratio on leaching of gold from mobile PCBs.

Table24 Result for gold leaching at different solid to liquid ratio

Sample [S2O3]2- [NH4OH] [Cu2+] Time Ratio Concentration of Gold %

(M) (M) (mM) (hrs) (S/L) Au solution (ppm) in

solution

1. 0.12 0.2 20 8 1/100 1.99 23.78

2. 0.12 0.2 20 8 1/50 2.11 25.00

3. 0.12 0.2 20 8 3/100 2.88 34.28

4. 0.12 0.2 20 8 1/25 0.49 5.83

5. 0.12 0.2 20 8 1/20 0.48 5.71

70
 40

35

30

25
Gold (%)

20

15

10

0
0 10 20 30 40 50 60

Solid to Liquid ratio

Liquid to solid ratio

Figure22. Effect of solid to liquid ratio on leaching of gold at 200 rpm for 8 hours.

From the graph we can infer that dissolution of gold has increased with increase in solid to liquid

ratio up to 30g/l and thereafter there is decrease in gold dissolution with further increase in solid

to liquid ratio. Maximum dissolution of gold is found to be at 30g/l. The reason for such a

behavior may be due to the fact that at low solid to liquid ratio sufficient PCB material is not in

contact with the thiosulphate solution and therefore leaching of gold is not sufficient while at

high solid to liquid ratio thiosulphate is not sufficient to leach gold.

Leaching of silver from mobile phone in ammonium thiosulphate solution

Table25 Result for silver leaching in thiosulphate solution

Elements Total Concentration in Concentration of elements leached % of metal

ppm ( as per literature) in thiosulphate solution (ppm) extracted

Silver 20 1.53 7.65 %

71
From the result shown in table above we can say that leaching of silver from mobile PCBs using

thiosulphate lixiviant is not very effective as only 7.65 % of silver can only be extracted. The

possible reason for low dissolution of silver may be the addition of copper ions into the solution

(Petter et al., 2014).

5.4. Analyzing toxic characteristics of gold leached solution by comparing heavy metal

concentrations in the solution with Toxicity Characteristic Leaching Procedure (TCLP)

and Central Pollution Control Board (CPCB) limits for hazardous material.

Printed Circuit Boards of mobile phones contain precious metals such as gold, silver, platinum

etc. along with other toxic heavy metals such as lead, chromium, zinc etc. Leaching of gold and

silver from mobile phones not only leaches out gold and silver but also toxic metals. Thus gold

leached aqua regia and thiosulphate solutions contain also toxic heavy metals along with gold

and silver. After extraction of precious metals from the solution, these spent liquors contain

several toxic metals. Classification of these spent liquors into “hazardous” or “non-hazardous”

categories will depend on the concentrations of toxic heavy metals.

Presence of some of the heavy metals along with their concentrations are tabulated below and the

element concentrations are compared with TCLP limits for Hazardous waste as well as CPCB

limits for listing hazardous waste for determining whether spent liquors fall in “hazardous” or

“non-hazardous” categories.

72
 Table26 Result for PCB leaching using aqua regia solution for some heavy metals.

Elements Aqua Regia Maximum concentration limits Federal TCLP Limits

Leaching determined by CPCB for listing for hazardous waste

(ppm) hazardous waste. (mg/l)

Cr 38.133 5 5

Zn 2540.85 250 NA*

As 0.0494 5 5

Pb 4025.50 5 5

Mo 12.902 350 NA*

NA*- limits were not mentioned by regulatory authorities

1- Published by USEPA under hazardous waste management section

2-Published in the gazette of India, extraordinary, part ii, section 3, sub-section (i), government

of India ministry of environment, forest and climate change notification.

From the above table we can see that concentrations of Chromium, Zinc, and Lead in Aqua

Regia spent liquor is higher than Maximum concentration limits determined by CPCB for listing

hazardous waste. Chromium and lead concentrations also exceed the maximum Federal TCLP

Limits for hazardous waste. Thus we can say that aqua regia spent liquor falls in the category of

“hazardous waste” and this solution has to be properly treated for Chromium, Zinc and Lead

elements before disposing of in the environment.

73
 Table27 Result for PCB leaching using thiosulphate solution for some heavy metals.

Elements Maximum Concentration in Federal Maximum

Concentration in solution having TCLP Limits concentration limits

thiosulphate maximum gold for hazardous determined by

solution (ppm) leaching (ppm) waste (mg/l) CPCB for listing

hazardous waste.

Cr 147.80 1.34 5 5

Zn 885.73 7.02 NA 250

As 1.27 < DL 5 5

Pb 142.04 142.04 5 5

Mo 2.80 < DL NA 350

NA- limits were not mentioned by regulatory authorities

1- Published by USEPA under hazardous waste management section

2-Published in the gazette of India, extraordinary, part ii, section 3, sub-section (i), government

of India ministry of environment, forest and climate change notification

From the above table we can see that the concentrations of Chromium, Zn and lead are greater

than the Maximum concentration limits determined by CPCB for listing hazardous waste. Also

we can notice that in thiosulphate solution having maximum gold dissolution, only Lead is found

to be crossing the Maximum concentration limits determined by Federal TCLP and CPCB for

listing hazardous waste. Therefore thiosulphate spent liquor has to be treated for Lead before

disposing of the solution in the environment.

74
5.4.1. Results of TCLP Test

Figure23 TCLP sample pH

The concentrations of elements leached through the method TCLP are indicated in below table, it

is clear evident that zinc leached most followed by lead and copper. On the contrast,

concentrations of arsenic, chromium and molybdenum are found to be well within the limits.

Overall, when comparing the leached concentrations with regulatory authorities like USEPA

which has listed allowable concentrations to not classify waste as hazardous under D-list and

CPCB standards for waste as hazardous waste, lead and copper have leached more than the

acceptable limits. So, the mobile PCBs sample can be classified as hazardous waste.

75
 TCLP Results

Table28 TCLP Results

Sl. No Elements Concentrations in ppm Average Standard Confidence UCL95 Federal Maximum

concentrations Deviation Limit TCLP CPCB Limits

Limits ( mg/l)

(mg/l)

1 Pb 82.01 80.08 80.03 80.71 1.13 1.28 81.98 5 5

2 Zn 91.01 92.48 92.93 92.14 1.004 1.14 93.28 NA 250

3 As 0.56 0.48 0.55 0.53 0.04 0.05 0.58 5 5

4 Cu 50.2 48.4 48.21 48.94 1.10 1.24 50.18 NA 25

5 Cr 0.05 0.06 0.05 0.05 0.01 0.01 0.06 5 5

6 Mo 0.006 0.005 0.006 0.01 0.0006 0.001 0.006 NA 350

NA- limits were not mentioned by regulatory authorities

1- Published by USEPA under hazardous waste management section
2-Published in the gazette of India, extraordinary, part ii, section 3, sub-section (i), government of India ministry of environment,
forest and climate change notification.

76
 100
90
80
Concentration in ppm

70
60
50
40
30
20
10
0
Pb Zn Cu
Elements

0.7

0.6

0.5
Concentration in ppm

0.4

0.3

0.2

0.1

0
As Cr Mo

Elements

Figure 24 TCLP result

77
5.5. Analyzing problems associated with implementing Extended Producer Responsibility

based e-waste management system in India.

5.5.1. Indian E-Waste Management system waste generation

Material and waste Generation

Figure25 First Stage of material & waste production

Up to this stage, there is no significant amount of e- waste generation. Market is organized to a

large extent, though not fully organized. A small amount of waste is generated in the
manufacturing stage but this waste is managed properly by manufacturer.

Figure26 Second stage of material& waste production

78
Table 29 Summary of Problem in e-waste management system in India and provision for the same in E-Waste management

rules 2011 and 2016.

Issues associated with Implications Provision in E-Waste Status of provision Recommendations

E-Waste Management Management Rules,

System in India 2016

1. Presence of powerful 1.Informal E-Waste 1. The role of various Implementation stage 1. Compulsory registration

informal E-Waste Recycling sector has stakeholders such as for recyclers as it will help

Recycling sector thwarted the manufactures, monitoring their activities.

development of Formal producers, traders, However, registration for

Recycling sector in India recyclers and kawadiwala is not required

government has been as no waste is generated in

2. Purely driven by clearly defined in collection phase.

economic interest developing formal e-

without having any waste recycling sector. 2.Role of local governments

concern for human However, there is no (Urban local bodies) should

health and environment provision which is be extended to the

79
 3. It has diverted the aimed at weakening monitoring and registration

flow of e-waste from the informal sector of recyclers

formal sector for

recycling

2. Low E-Waste 1. Many of the formal E-waste management For the first two years a 1. Retail Outlets can be used

Collection efficiency in Recycling Units are Rule 2016 has collection target of 30% for collecting e-waste.

formal sector underutilized because of provision for of the quantity of waste Switzerland E-Waste

shortage of e-waste as collection of e-waste generated as indicated in Recycling system has

input for the unit. separately from other Extended Producer effectively utilized this

2. Resulted in the solid wastes seeing its Responsibility has been option.

closure of many toxic characteristics. set. 2. Public places such as

recycling plants. 2. It has made railway station , bus stop,

3. Discouraged new manufactures commercial complexes can

entrepreneurs in responsible for the also be provided with e-

establishing new take back for their waste collection facilities as

recycling plants products after its end has been done in

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 of life period (EoL). Switzerland

3. Targeted approach

has been opted for

collection of e-waste

3.Reluctance of 1. It has resulted in 1. Responsibilities of The system is still in 1. Producers &

producers and producers and initial stage and it is too manufactures should

manufacturers in manufactures have early to specify its status voluntarily come forward

performing their duties been clearly defined and actively participate in

regarding to collection developing formal recycling

and recycling of e- sectors as is the case with

waste generated by Switzerland. This will help

them producers to developing a

system which will be

flexible and sensitive to

their interests which will

81
 not be the case if they

follow the system proposed

by the government

4.Low Information 1. Lack of coordination 1. No adequate Nil Learnings from Switzerland

Flow between various stake provision in E-waste e-waste management system

holders such as management rule 2016 reveal that information flow

producers, for smooth flow of is vital for stability and

manufactures, recyclers information between functioning of formal

& dismantlers. stakeholders at various recycling sector

levels

2. It has thwarted the

functioning of formal e-

waste recycling system

in India

82
5. Lack of awareness 1. Reduces e-waste 1. Role and Though awareness about 1. Awareness about toxicity

about hazardous nature collection efficiency as responsibilities of environment cleanliness of e-waste should be

of e-waste among many WEEE remain individual and bulk is being generated generated by government.

consumers. there in homes and don’t consumers have been through advertisements

reach to reach to clearly mentioned in under “Swachh Bharat 2. Academic institutions can

recycling sectors the E-waste Mission”, no awareness play very important role in

Management Rule about toxic generating awareness in rural

2. Most of the e-waste 2016. characteristics associated areas by organizing camps

land up in informal sector with e-waste is being during vacations.

instead of landing in generated through 3.Research studies should be

formal sector advertisements as of done to study consumer

now. behavior in dealing with e

-waste

83
5.5.2. Hurdles in implementing EPR based E-Waste management systems in India.

1. Presence of powerful informal e-waste recycling sector

2. Reluctance of manufacturers to mutualize their responsibility.

3. Unorganized new electronic goods market.

4. Low government participation

5. Lack of coordination & information flow between stakeholders.

6. Flow of e-waste from developed countries.

7. Consumer behavior.

8. Insufficient recycling Infrastructure

5.5.3. Recommendations for setting up EPR based E-Waste management system.

1. Integration of informal recycling sector to formal sector.

Reasons

i. Huge network coverage and high collection efficiency

ii. Huge employment generation potential

2. Setting up Producer Responsibility Organization without involving government.

Reasons

84
 i. Associations such as EWAIN, ELCINA etc should take the responsibility of setting

PROs.

ii. This will ensure flexibility in the system

iii. Help manufacturer design better products.

iv. Can be started without taking every manufactures into consensus.

3. Proactive role for the government.

To integrate informal sector to formal sector through Compulsory registration for

recyclers/Dismantlers, transporters but not for collectors, tax credit benefits and Regular

supervision

Figure27 Role of ULBs

4. Responsibilities of PROs in India.

i. To set up formal recycling system in India by bringing together various stakeholders

manufacturers.

ii. To create Recycling money fund by through ARF tools

85
iii. Fixing ARF with the help of external auditors.

iv. Come out with proper mechanisms to ensure compliance of stakeholders.

v. Competitive bidding for recyclers

vi. Create awareness about e-waste.

86
 CHAPTER 6

SUMMARY, CONCLUSION AND FUTURE WORK

6.1. Summary and conclusion

In this work, laboratory experiments were conducted to study the effectiveness of ammonium

thiosulphate in leaching gold and silver from mobile printed circuit board. The effect of copper

sulphate as an oxidizing agent was also analyzed. Mobile PCBs were first characterized with

aqua regia solution to get an idea about maximum leaching of precious metals and then with

thiosulphate.

The use of aqua regia as lixiviant showed good result for gold leaching with gold dissolution at

72.68% while silver dissolution was found to be not satisfactory as it was mere 31.15%.

The best result for leaching of gold from mobile PCBs using ammonium thiosulphate was found

with a solution having 0.08 M thiosulphate, 0.1 M ammonium hydroxide and 20 mM copper

sulphate. Gold dissolution was found to be good at low thiosulphate concentration and gold

leaching decreased with increase in thiosulphate concentration. The effect of solid to liquid ratio

on leaching process was also analyzed and the maximum leaching of gold was found at liquid to

solid ratio of 30g/l. Silver dissolution with ammonium thiosulphate was found be very low. The

maximum silver leaching was found to be just 7.65 %.

Mobile PCBs were also characterized for some heavy metals to analyze the toxicity of extract

solution. It was found that aqua regia extract solution has higher concentrations for Chromium,

Lead and Zinc than the maximum limits set by CPCB for listing hazardous waste. When

compared with Federal TCLP limits concentrations of Lead and Chromium was found to be

higher. Thus aqua regia falls under the category of “hazardous waste”. Thiosulphate extract

87
solution was also found to be hazardous as it had higher concentrations of Lead and Copper than

the permissible limits set by CPCB and Federal TCLP procedure.

This paragraph deals with the result conclusion of the third objective of the study. The study of

electronic waste management system in Switzerland cannot be replicated blindly, yet learning

from this system can be applied universally. The findings from the study which can help policy

makers in India devise a fully functional and self reliant e-waste management system are as

follows:

First, the way producers/manufacturers of EEE items took initiative to develop formal e-waste

management system in Switzerland; likewise in India also producers should come forward and

take responsibility of developing a system to ensure proper recycling of e-waste. For example

Electronic Industries Association of India (ELCINA) can be assigned the responsibility to bring

various actors under one platform.

Second, even though India does not a formal waste collection system, waste collection

efficiency is high in India. This is because informal waste collection system is well developed

and its rural as well as urban penetration is high. Therefore, instead of developing a separate e-

waste collection system, the focus of policy makers should be on integrating informal sector with

the new waste management system. However, care should be taken that the collection system is a

comprehensive one covering all types of electrical and electronic goods.

Third, to ensure compliance of stakeholders and transparency of the system, a proper control

mechanism should be devised out. This will require legislative support defining penalties for

various actors in case of non compliance.

88
Fourth, Registration should be made compulsory for dismantlers and recyclers but not for waste

collectors. This is because collection stage does not generate any toxics to the environment

whereas recycling stage is associated with generation of pollutants. Registration of recyclers will

thus not only help in monitoring pollutant release into the environment but also communicating

guidelines and policy initiatives of the government. On the other hand, registration of waste

collectors will decrease collection efficiency.

Fifth, E-Waste management should be as market oriented as possible to ensure financial

reliability of the system.

6.2. Directions of Future work

From the study we found that the result of thiosulphate leaching of gold was not satisfactory and

therefore more studies should be carried out to make thiosulphate a viable option for gold

leaching. To increase dissolution of gold using thiosulphate following studies may be carried.

i. Use of hydrogen peroxide along with copper sulphate as oxidizing agent.

ii. Oxidative leaching of copper from mobile PCBs prior to the leaching of gold.

iii. Multiple leaching of mobile PCBs

Future work regarding E-Waste management in India has been summarized as follows:

First, gathering data on e-waste generation and developing e-waste management database.

Second, to develop System dynamic model for material and financial flows. This will help in

designing and evaluating new policy measures for improving existing e-waste management

system (Sterman, 2001). Third, further research on the effectiveness on policy instruments

should be carried out.

89
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95