“The informaTion age’s Toxic garbage”
A review of electronic waste
(e-waste)
recycling technologies
“is e-wasTe an opporTuniTy or TreaT?”
Prof.Dr. Muammer Kaya
Eskişehir-Osmangazi University
Technological Research Center (TEKAM)
Eskişehir-TURKEY
WHAT IS e-WASTE?
(Discarded/EOL electronics)
• Since the 1980’s, with the development of consumer-oriented
electrical and electronic technologies, countless units of electric and
electronic equipment (EEE) have been sold to the consumer.
 When electronic products become obsolete and are ready for
disposal, they are known as e-waste.
 Whether generated at home/office, e-waste is most rapidly growing
waste problem in the world (20-50 million t/y (UN))
 Information technology and electronic industry are the world’s largest
and fastest growing manufacturing industries.
 But to date, industry, government and consumers have only taken
small steps to deal with this looming problem.
 Developed countries that use most of the world’s electronic products,
generate most of the e-waste, and tried to solve this problem by
exporting hazardous e-waste to the poor countries in Asia and Africa.
WEEE CLASSIFICATION OF e-WASTE (2003)
WEEE Category
Rate of Recovery
Rate of Reuse
& Recycling
1. Large household appliances (ovens, refrigerators,
driers, washing machines, air conditioners etc.)
80%
75%
70%
50%
75%
65%
75%
65%
5. Lighting equipments (mainly fluorescent tubes/
bulbs) (gas discharge lamp 80%)
70%
50%
6. Electrical and electronic tools (E-tools) (drilling
machines, electric lawnmowers etc.)
70%
50%
70%
50%
2. Small household appliances (toasters, vacuum
cleaners, mixers, ovens etc.)
3. IT& telecommunication appliances (PCs, desk
tops, lap tops, printers, phones, scanners, mouses,
faxes, photocopy machines, computer peripherals,
wireless devices etc.)
4. Consumer equipments electronics (TVs, flat
panels, plasmas, LCDs, HiFis, portable CD players,
DVDs, VCDs, iPods, MP3s, PDAs etc.)
7. Toys, leisure & sports equipments (electronic toys
training machines etc.)
8. Medical devices
Microscopes etc)
9. Monitoring
GPRS etc)
control
MRI,
EKG,
instruments
SEM,
To be established by end of 2008
(Lasers,
70%
50%
10. Automatic dispensers (ticket issuing, vending
machines automats etc.)
80%
75%
EU-27
and
(X-Ray,
E-waste amount was 8.3 million t in 2005
collected 2.2 million t
E-waste amount will be 10 million t in 2011
collected 5.3 million t
WHY e-WASTE IS A PROBLEM?
• Serious problem not only quantity but also toxic ingredients (such
as Pb, Hg, Cd, Cr, brominated flame retardants (BFR)) which create
occupational and environmental health threats and hazards.
• E-waste contains over 1000 different substances many of them are
toxic and creates serious pollution problems upon landfilling/burning.
• Life span of EEEs is shrinking&obsolescence rate is increasing.
• Replacement of EEE’s are easier/cheaper than repair them.
e-WASTE DISPOSAL METHODS
(BASEL CONVENTION bans the transport/export of hazardous material from rich to poor
countries and 170 countries signed the convention)
NEW WASTE MANAGEMENT
OPTIONS/TECHNOLOGIES
(expensive but environment friendly)
CONVENTIONAL
(Cheap but not environment friendly
(contaminate ground water, soil and air)
I. LANDFILL (contaminate ground water)
II. STABILIZING (requires pretreatment and
expensive)
III. INCINERATION/BURNING
(releases
metals/ashes/gases)
IV. EXPORTING TO THE POOR
COUNTRIES (cheap, easy)
(Disposal of e-waste to the MSW is
prohibited today)
I. RECOVERY (collection, sorting)
II. REUSE (resell, second-hand use)
III. RECYCLING (valuable materials are
recovered by hydro, pyro and
electro metallurgical methods)
* example: Umicore (recycled 1% of
cellphones in the world in 2006)
Financement:
-
Advanced Recycling Fee (ARF): (Swico)
(consumer pay 7-30 $)
Extended Producer Responsibility (EPR)
TakeBack (GreenPhone, Collective
Goods)
Tax Incentives (Credit)
SOME FACTS ABOUT e-WASTE IN THE WORLD
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According to EPA, yearly e-waste produced in the USA is estimated 5-7 million tons. Only
20% of these are recycled, 30% or more stored 3-5 years for future disposal and the rest is
land filled/exported.
E-waste constitutes from 3-8% of the U.S.-MSW and is growing rapidly.
Approximately 25 million TV sets and 50 million computer monitors are sold in the USA
annually. According to EPA, yearly 30-40 million PC become obsolete in the U.S.
Computer industry brings new technology on market every 18 months. Conventional TV
sets will be replaced by HD TV’s (25 million TV/year) which will put millions of kilos of CRT
Pb (leaded glass) into environment.
In the USA, Americans own about 2 billion electronic devices or 25 per household.
130 million cell phones are retired each year in the USA. Yearly 3 billion batteries and 80
million automotive batteries are sold in the USA.
In 1999, only 11-15% of discarded computers are recycled compared with 70% of the major
appliances (refrigerators, washing machines, dryers etc) and 28% of overall MSW.
In the USA, btw 50% and 80% of collected e-waste for recycling are not recycled domestically at all; but, shipped to poor countries (China, India, Nigeria, Ghana, Ivery Coast,
Lagos etc.).
In Europe, the volume of e-waste is raising 3-5% annually almost three times faster than
the MSW.
In EU, 6.5 million tonnes of e-waste generated annually. The battery consumption per
person is about 10 in Europe.
E-WASTE MARKET generated $7.2 billion in 2007 and will be expected to generate $11
billion in 2009 (Yearly growth: 5-8%).
HAZARDOUS MATERIALS IN THE e-WASTE
(Electronic products/components contain, chlorinated solvents, BFR, PVC, heavy metals, plastics and glasses)
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•
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•
•
Computer circuit boards: Pb, Cd
Computer batteries, semi conductors: Cd, Ni
Printed circuit boards, cables and plastic
casings: BFRs, Sb2O3, PVC (when burned
releases toxic furans and dioxins)
Switches, flat screens, housing: Hg
Old capacitors/transformators: PCBs
CRT glass: Pb (%25), Ba, As
Power suppy: Se
Stell parts: Cr (corrosion), Co (magnetivity)
Lead (Pb): cause damage to the nervous and
blood systems and kidney in humans,
accumulates in the environment, and has
acute and chronic toxic effects on plants,
animals and microorganisms. Children
suffer developmental effects and loss of
mental/brain ability, even at low levels of
exposure.
Consumer electronics constitute 40% Pb
found in landfills. The main concern in
regard to the presence of Pb in landfills is
the potential for the Pb to leach and
contaminate drinking water supplies. The
main applications of Pb in electronics are
soldering of printed circuit boards and other
electronic components and CRTs.
Composition of a personal desktop computer
based on a typical desktop computer, weighting ~70lbs
Name
Content
(% of total
weight)
Recycling
Efficiency
Use/Location
plastics
22.9907
20%
includes organics, oxides other than silica
lead
6.2988
5%
metal joining, radiation shield/CRT, PWB
aluminum
14.1723
80%
structural, conductivity/housing, CRT, PWB,
connectors
germanium
0.0016
0%
semiconductor/PWB
gallium
0.0013
0%
semiconductor/PWB
iron
20.4712
80%
structural, magnetivity/(steel) housing,CRT, PWB
tin
1.0078
70%
metal joining/PWB, CRT
copper
6.9287
90%
conductivity/CRT, PWB, connectors
barium
0.0315
0%
getter in vacuum tube/CRT
nickel
0.8503
80%
structural, magnetivity/(steel) housing,CRT, PWB
zinc
2.2046
60%
battery, phosphor emitter/PWB, CRT
tantalum
0.0157
0%
capacitors/PWB, power supply
indium
0.0016
60%
transistor, rectifiers/PWB
vanadium
0.0002
0%
red phosphor emitter/CRT
terbium
0
0%
green phosphor activator, dopant/CRT,PWB
beryllium
0.0157
0%
thermal conductivity/PWB, connectors
gold
0.0016
99%
connectivity, conductivity/PWB, connectors
europium
0.0002
0%
phosphor activator/PWB
titanium
0.0157
0%
pigment, alloying agent/(aluminum) housing
ruthenium
0.0016
80%
resistive circuit/PWB
cobalt
0.0157
85%
structural, magnetivity/(steel) housing,CRT, PWB
palladium
0.0003
95%
connectivity, conductivity/PWB, connectors
manganese 0.0315
0%
structural, magnetivity/(steel) housing,CRT, PWB
silver
0.0189
98%
conductivity/PWB, connectors
antinomy
0.0094
0%
diodes/housing, PWB, CRT
bismuth
0.0063
0%
wetting agent in thick film/PWB
chromium
0.0063
0%
decorative, hardener/(steel) housing
cadmium
0.0094
0%
battery, blu_green phosphor emitter/housing, PWB,
CRT
selenium
0.0016
70%
rectifiers/PWB
niobium
0.0002
0%
welding allow/housing
yttrium
0.0002
0%
red phosphor emitter/CRT
rhodium
0
50%
thick film conductor/PWB
platinum
0
95%
thick film conductor/PWB
mercury
0.0022
0%
batteries, switches/housing, PWB
arsenic
0.0013
0%
doping agents in transistors/PWB
silica
24.8803
0%
glass, solid state devices/CRT,PWB
The EU’s
Waste Electrical and Electronic Equipment (WEEE)
and
Restriction of Hazardous Substances (RoHS) Directives
The WEEE Directive requires that producer is responsible for the
treatment of WEEE. The directive also requires labeling of ewaste identifying the different components and materials within
those components.
The RoHS takes prevention a step further by phasing out the use
of hazardous substances in the production of EEEs by 2008.
Hazardous Material Limits (%) at
WEEE according to RoHS Directive
Cadmium
0.01
Lead
0.1
Mercury
0.1
Hex. Cr
0.1
PBB
0.1
PBDE
0.1
FLOWSHEET OF e-WASTE RECYCLING
Test/Sort
COLLECTION: Permanent, special dropoff and curbside metods.
TRANSPORTATION: to the recyclers by
customers, municipalities or
recyclers
MATERIALS RECOVERY FACILITY (MFR):
1. Testing and sorting for reuse/resale,
2. Manual/mechanical dismantling of
valuable parts from cheap/valueless
ones,
3. After removing hazardous substances,
valuable materials are recovered by
magnetic, gravity, eddy current,
flotation separation methods,
4. Hydro/pyro metallurgical smelting&
leaching and refining&conditioning,
5. SECONDARY RAW MATERIALS are
produced for use.
6. Final waste is disposed by landfilling/
burning.
CATHODE RAY TUBE (CRT) RECYCLING SOLUTIONS-1
(Monitors-Screens-Displays)
•
- contain toxic items, - volume is high, - direct disposal restricted.
• - consists of two parts: glass components (funnel, panel, solder
glasses and neck) and non-plastic components (plastic, steel,
Cu, electron gun, P coating)
• - CRT glass consists of SiO2, Na2O, CaO and other
components for coloring, oxidizing and X-rays protection (K2O,
MgO, ZnO, BaO and PbO).
• There are two CRT recycling methods: glass-to-glass (GTG)
and glass-to-lead (GTL).
•
CATHODE RAY TUBES (CRT) RECYCLING SOLUTIONS-2
(CRTs contain 0.5-5 kg Pb in the glass for X-ray protection and 1- 2.3 kg Cu in the yoke)
1. GTG Recycling: Closed loop recycling (from used
CRT to new CRT(up to 40%)). Labor intensive
and expensive method.
a. Shredding: CRT is ground as a whole into cullets,
which are used to make new cullets to replace
the virgin material (mixed cullets sold to
smelters)
b. Sawing: Panel and funnel glasses can be
separeted to avoid contamination (sorted
cullets sold to smelters)
(Leaders: Eco-International (2007) (NxTCycle-AZ,
Envirocycle-PA (1991), Amandi), Dlubak GlassOh/AZ (Largest recycler-10% of US CRTs).
2. GTL Recycling: Automated, cheap, safe, efficient;
but, reduces the high-quality of glass
Before smelting, the CRT is shredded, Pb and Cu
metals and plastics are separated. Recovered
CRT glass goes to the Pb smelter and it behaves
as a fluxing agent in the smelting process.
(Ex: Doe Run (World’s largest secondary Pb
smelter), Noranda (Xstrata)
Rival to CRT Recycling: 10 times cheaper overseas
recycling. Shipping cost is cheap with empty
containers to China
CRT
Liquid-Crystal Dispays (LCD) and Plasma Screen (Flat Sceen-HDTV)
CATHODE RAY TUBE (CRT) RECYCLING-3
(Exporting CRT with
containers to Asia is ten times cheaper than recycling in the
USA)
CRT Glass Processing at Dlubak
CRT take apart for panel and funnel glass
Panel glass sorting by composition
Glass cleaning, crushing, and sorting by size
Ferrous and non-ferrous metal removal
Organic contaminant removal
CHINA
S.AFRICA
BATTERY RECYCLING
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Hazardous automobile Pb-acid battery
recycling ratio is 90% in the U.S..
In US annually 3 billion, in Germany
31000t in England 20000t and in Turkey
11000 t household batteries are used.
Household batteries may contain Pb, Zn,
Cd, Hg, Ni, As, Mn, Cr etc.
88% Hg and 54% Cd, in MSW in the U.S.,
10% Zn, 67% Ni and 85% Cd in MSW in
Germany come from batteries.
In EU, 75% of batteries used at home and
95% of batteries used at industry will be
collected and recycled soon.
Recycling of mixed batteries are difficult
and present vapor hazards.
Alkaline, Zn-C, NiCd, Lion, NiMH,
mercuric oxide and silver oxide button
batteries are recyclable.
NiCd batteries are more hazardous than
NiMH and Lion batteries.
There are several hydro/pyro metalurgical processes for battery recycling
(Sumitomo, Recytec, Atech, SnamSavam, Sab-Nife, Inmetco, Waelz, TNO
and Accurec etc).
Recycling fee changes from 300-2000 $/t.
Battery recycling requires a high amount
of energy.
Alkaline and Zn-C Batteries Recycling Flowsheet
Umicore VAL’EAS Battery Recycling Process & Flow Sheet
The VAL’EAS™ process is dedicated to the recycling of
rechargeable Lithium ion and Nickel Metal Hydride
batteries and battery packs, transforming end of life
rechargeable batteries into new batteries.
a melting operation: rechargeable batteries, battery
packs and other input materials are injected into a
furnace without any pre-processing, minimising all
hazardous risks
a preferment gas cleaning of installation equipped with
the new plasma technology to make the formation
dioxin and furan impossible
well controlled melting conditions so that a clean slag
can be produced and further re-used in
construction and/or as aggregate for concrete.
a cobalt & nickel refining installation where the cobalt &
nickel containing alloys can be further treated so
that pure cobalt and nickel are prepared.
followed by a process for transformation of cobalt
products into the final lithium cobalt dioxide
LiCoO2 which is then used in the production of new
lithium ion batteries.
By developing and patenting a sustainable and costefficient VAL’EAS™ battery recycling process,
Umicore is the only company in the world
proposing a real closed loop solution for Li-ion
batteries combined with an environmentally sound
management of these end-of-life batteries and high
recycling and/or recovery rates.
MIXED PLASTIC WASTE RECYCLING SOLUTINS-1
(plastic is visible or hidden in the EEE due to insulation, strength,
resistance, flexibility and durability)
Thermoset plastics can’t be remelted and formed
into new products (circuit boards, switch
housings, electrical breakers etc)
Termoplastics can be remelted and formed in new
products.
Recyclibility of termoplastic resins is better
than termoset resins.
TVs: HIPS, ABS, PPE, PVC, PC
Computers: ABS, HIPS, PPO, PPE, PVC, PC
Micellaneous EEE: HIPS, ABS, PVC, PPE, PC
Composition of consumer electronic
plastic resin
There are 3 ways of post consumer plastic
recycling in the EEE.
1. Chemical Recycling: Use mixed-waste plastics as raw
materials for petrochemical processes or as a
reductant in a metal smelter. There are 3 processes
HIPS: high impact polystyrene, ABS: acrylonitrile butadine
styrene (impact protection), PPO: polyphenylene oxide
(high temperature), PE: Polyethylene , PVC: polyvinyl
cholaride (insulator), PC: polycarbonate, PPE: poly-
a.Depolimerization and Conversion (350-400 C) (Syncrude
oil (80%), gas (10%) and solid waste (10%) are
produced and sent to petrochemical proceses).
b. Coke Oven Process (carbonization, products are 20%
coke, 40% tar, %40 gases (metan and
hydrogen)(Japan-Nippon Steel) .
c. Reducing agent for Fe2O3 (instead of coke) in blast
furnace (Sweden).
MIXED PLASTIC WASTE RECYCLING SOLUTIONS-2
2. Flowsheet of Mechanical Recycling
of Mixed Waste Plastics
3. Thermal Recycling of Plastics: Plastic is
used as fuel to generate energy.
(1 t EOL plastic = 1.3 t coal in cement kilns)
Remove paint, coatings
(Crygenic grinding, abrasion, solvent stripping etc.)
Shear shredder,
hammer mill,
Granulators,
mills
(liberation)
Foreign
materials
separation
Triboelectric Separation
Switzerland and Denmark thermally recover
70% of their waste plastic in 2002.
In 2003, 23% of total waste plastic of West
Europe thermally recycled which is the
largest portion in recycling methods.
Solid plastic waste combustion facility must
have wet scrubber (APME).
MARKETS FOR RECYCLED PLASTICS
One third of materials in EEE devices is
plastic but only 25% of that is clean,
homogenous and free from
contamination.
Swiss Results Technology
Inc. (Circuit board plastics
separation)
MBA Polimers Inc. (HIPS
from TVs)
Recycled plastics are used for plastic
lumber, outdoor furniture, roadbed fill,
battery boxes, compact disc trays,
camera casings, laminated floorings,
automotive parts, pellets, carpet, fabric,
fiber, geotextile, desks, trays, bottles
etc.
METALS RECYCLING IN EEE WASTE-1
Permanent/Electric Magnetic Separation: Ferrous metals (Fe&steel),
Eddy Current Separation: Non-magnetic metals (Al, Cu) (Conductivity/Density ratio)
SECONDARY LEAD (Pb) RECOVERY
- In the reverberatory/rotary furnace,
Pb containg material is reduced to
soft Pb bullion (99.9% Pb) by coke
and foreign materials are oxidized as
slag (60-70% Pb).
(Pb Bullion)
low Sb
Dust in the flue
gas are collected
by baghouse
(%60-70 Pb)
Iron and
limestone
(fluxing)
Energy Saving: 15-40%
Britannia Refined Metals (BRM) (UK) Isasmelt Plant Schematic Diagram (30000 tpa)
High Sb
Desulphurisation by Na2CO3/NaOH to form Pb-oxide and Na2SO4
(15-25% Sb)
87%
Final slag
13%
Kettles
12.4%
Pb Distribution
0.6%
1991
1-3% Pb, CaO,
SiO2, FeO
(Disposed of
landfills)
METALS RECYCLING IN EEE WASTE-2
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SECONDARY COPPER (Cu) RECOVERY
5-40% Cu containing electronic scrap are
fed into a blast furnace. Cu-compounds
have to be reduced by scrap Fe and
plastics. Sn, Pb and Zn impurities are
also reduced as gas fumes.
Energy needed to reclaim Cu from EOL ewaste is only one sixth of the energy that
would be required to produce from Cu
ore.
Scrap Fe,
plastics
Impurities
(Sb, Pb, Zn)
burned, Fe
goes to slag
Scrap Cu
Air/O2
(Coke, wood
or plastic)
H2SO4
Slag: roof
shingles, sand
blasting and
blasts for
railroads
Burning cables for Cu
Ni, Zn, Fe
removed
Slimes
METALS RECYCLING IN EEE WASTE-3
PRECIOUS METALS RECOVERY
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Au, Ag, Pa and Pt are recovered from
anode slime of Cu electrolysis process
by pressure leaching.
The leach residue is then dried and
smelted with fluxes in the furnace.
During smelting Se is recovered; from
remaining material, Ag is cast into Ag
anode.
After high-intensity electrolitic refining, a
high-purity Ag cathode and Au anode
slime are formed.
Anode Au slime is then leached and high
purity Au, as well as Pa and Pt sludge are
precipitated.
Se
One third of the precious metals recovered
from e-waste are Au, as electronic scrap
contains more than 40 times the Au
contained in Au ores in the U.S.
Recovering precious metals from
e-waste is one of the greatest
economic profits for recycling
industry in the world.
PRECIOUS METALS REFINARY PROCESS
SOME LEADING
E-WASTE
RECYCLERS
RECYCLER
CAPACITY
E-WASTE
PRODUCT(S)
SIMS E-Recycling
(Hydromet/Simsmetal),
Unanderra, NSW,
Australia (2006)
36000 t/y battery
20000 t/y Pb
2.4 million battery
(30%)
Used Pb-acid
battery (ULAB)
Pb metal (plates)
Lead oxide (paste)
PP (casings)
Weak acid (H2SO4)
Sold to the secondary
lead smelters
Umicore
Antwerp
Belgium
(1887)
World’s largest
precious metal
recycler
Lion and NiMH
batteries
Cellphones
TVs, laptops
Precious metals
(Ag, Cu, Pt, Au etc)
(17 metals)
Val’eas process (won
EEP gold award in 2004)
(Best Available
Technology- BAT)
Metech Inc. (CERLSingapore)
(Gilroy CA, Worchester MA, Durham
NC) (USA) (1968)
Engitech SpA.
Italy
1973
Electronic
recycling and
precious metal
refining
Computer
recycling
Precious/base
metals, plastics,
glass
ISO 9001-14001
Certified destruction
and meterial recovery
Used Pb-acid
battery
(55% Pb, 5%
PP
Secondary Pb
production
Na2SO4/(NH4)2SO4
(fertilizer grade)
3-50 t/h
PROCESS
Local dealers
Paste desulphirisation
(CX), CX-EWS or
Fluoborik (HBF4)
hydromet. Technology.
Safest, cleanest, cost
effective
RECYCLER
CAPACITY
E-WASTE
PRODUCT(S)
50 million
batteries
10 recycling
facilities (6 in
USA, 3 in EU and
1 in New Zealand)
Used Pb-acid
battery (ULAB)
Pb metal (plates)
Lead oxide (paste)
PP (casings)
Weak acid (H2SO4)
Sold to the battery
plants
Cases, covers for new
batteries
BSB
Braubach-Germany
(1985)
80000 t/y battery
40000 t/y Pb
Used Pb-acid
battery (ULAB)
24000 tpa Pb, 15000
tpa Pb bullion, 1000
tpa Sb alloy, 35000
tpa PP
Paste desulphurisation
with Na2CO3
CX
Tonolli
Mississauga- Canada
(1988)
60000 t/y battery
20 million
batteries
Used Pb-acid
battery
Pb metal and Pb
alloys (30000 t/y
rafined Pb)
Hydrodynamic separator
Paste desulphirisation
(Engitec-CX),
Safest, cleanest, cost
effective
Exide Technologies
One of the largest
secondary Pb recycler
in the world)
7100 tpa Na2SO4
(detergent/glass
grade)
3000 tpa PP
2000 tpa ebonite
PROCESS
CONCLUSIONS
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Technological revolution produces faster, smaller and cheaper EEEs. E-waste is
inevitable by-product of an exponential evolution of personnel electronic
appliances.
E-waste reduction and producer responsibility from “cradle-to-grave” are
becoming important.
Extended Producers Responsibiity “Take it back, make it clean and recycle”.
Producers should design their products with longer life-span and increased
recyclibility.
E-waste recycling infrastructure for collection and processing are not well
established in the world yet.
Exporting e-waste to overseas and using women/prisoners/childreen are not
right, fair and humanistic solution.
Current recycling techniques are expensive, not automated and depend on
mostly manual operations.
Use Best Available Hydrometallurgical Technologies (BAT) rather than
pyrometallurgical Technologies in e-waste recycling.
4-6 kg WEEE should be collected per person and 75% of this must be recycled
each year in any country.
Apply “Reduce, Reuse and Recycle (RRR)” waste management hierarchy.
Countries must obey the Basel Convention, WEEE and RoHS directives.
E-waste recycling not only protects environment, but also saves energy and
raw materials.
E-waste recycling market will be a promising sector in the near future.
THANK YOU for LISTENING
Prof.Dr. Muammer KAYA
Eskişehir-Osmangazi University
TECHNOLOGICAL RESEARCH CENTER
(TEKAM), TURKEY