Lecture 6

Thermal Treatment of
Hazardous Wastes

1
1. Introduction

• Incineration systems are designed to destroy only

organic components of waste, but most HWs
contain both combustible organics & non-
combustible inorganics
• By destroying the organic fraction and converting it
to CO2 and water vapor, incineration reduces the
waste volume and the threat of toxic organics to
environment.
2
 1. Introduction
• Good combustion is good oxidation of the
organic components; C & H.
• To achieve this, air must be thoroughly mixed
with the C and H of the waste to produce a
stoichiometric product of CO2 & H2O.

3
 1. Introduction

• The complete oxidation of C and H occurs at

some prescribed Time, Turbulence (Mixing)
and Temperature.
• Decrease one of these factors, the other two
must be increased to achieve the same
combustion efficiency.

4
 2. Combustion

Typical combustion process reactions

• C + 2(O2 + N2)  CO2 + 2N2 + O2 + Heat
• H2 + 2(O2 + N2)  H2O + 2N2 + 3O2 + Heat
• CH4 + 3(O2 + N2) CO2 + 2H2O + 3N2 + O2 + Heat
• Combustion of HWs does not differ from combustion of fuels except
that HWs contain many different organics.
• Every waste has a measurable heating value (Btu/lb) which can be
determined by bomb calorimetry.
• The heating values of most common waste chemicals and mixtures are
available from the literature.
• Unfortunately, air also contains 79% N2, which is inert
and gets in the way of the combustion process.

5
Excess air

• When organic wastes are burned with a stoichiometric

amount of O2, the products should not include any O2.
• Perfect combustion is an infinitely narrow line between
excess- and starved-air combustion (pyrolysis) and is
not possible in commercial burners or incinerators.
• Incinerator's must always utilize excess air to achieve
combustion; however, they may accomplish this in two
stages-the first stage operating under starved air
(pyroliticaIly) and the second with an excess of air.

6
 Wastes containing sulfur, halogens, nitrogen and inorganics

• Combustion of wastes containing sulfur produces SO2.

• Halogen containing wastes (Cl, F & Br) produce the acid
halogen gas (HCI, HF and HBr) in a combustion reaction.
• Nitrogen compounds in the fuel present a complication
because they form NOx during combustion.
• NOx (NO & NO2) are also formed in combustion of fuels
that do not contain N by a process called N-fixation.
• NO2 is not generally present in flue gases above 1200°C.
• NO is the predominant NOx in the flue gas.

7
 Metals
• Inorganic components of wastes fed to an
incinerator cannot be destroyed, only
oxidized.
• Metals that enter combustion process as a
component of HW exit as metal oxide.
• If the metal enters the process as a metal salt
that has a boiling point lower than incinerator
temperature, it may vaporize, not oxidize and
therefore be present in flue gas

8
 3. Gases and Vapors

• Waste gases usually consist of a hydrocarbon or a

mixture of hydrocarbons in air.
• They may be in such high concentrations that ignition
is not possible until more air is added and are called
above the higher explosive limit (HEL).
• Mixtures of hydrocarbon vapors in air that can be
ignited are called within the explosive range.
• Mixtures with low hydrocarbon concentrations that
cannot be ignited are called below lower explosive
limit (LEL).
9
 4. Catalytic VOC incinerators

• Low concentrations of VOC in air can be

effectively removed by catalytic incineration.
• VOC-air stream is heated to a temperature at
which the VOC will begin to bum on the surface
of the catalyst.
• The catalyst (a noble metal, e.g., Pt or Pd)
enhances the combustion reaction and causes
oxidation of VOCs on the catalyst surface with
very little heat loss.
10
 Thermal VOC incinerators
• No catalyst is used to remove the VOC in air.
• The incoming VOC-air mixture must be heated
to a temperature where the VOC will be
oxidized.
• Most VOCs are reduced to desirable levels at
exit gas temperatures of 815 oC.

11
 Determination of HW properties
• The following information on the waste to be burned in
the incinerator is required to design and properly
engineer the total system and the auxiliary components.
• Chemical composition
• Heat of combustion
• Corrosivity
• Reactivity
• Potential for polymerization
• Ash content

12
 Lecture 7

Land Disposal (Land Filling)

13
 Introduction
• Landfills are designed and constructed to contain
discarded waste so as to minimize releases of
contaminants to the environment.
• They are a significant part of HW management
because;
• other HW management technologies such as source
reduction, recycling, and waste minimization cannot
totally eliminate the waste generated and
• HW treatment technologies such as incineration
and biological treatment produce residues.
14
 Hazardous waste Landfill operations

 Before landfilling the following information

should be taken
• who provided the waste,
• the nature of the waste, and
• where and when the waste was landfilled.

15
 Advantages of Land Disposal
• Controls animals and vectors (disease).
• Protects the public from results of direct contact with
HW
• Controls gas movement to avoid a decline in air quality.
• Minimizes fire potential to avoid air emissions and
damage.
• Controls surface water runoff.
• Resists erosion.
• Minimizes noxious odors.

16
Land Disposal System

17
 Land Disposal System

• The uppermost layer, a vegetation support layer,

typically consists of an organic sandy loam (topsoil)
material used to support vegetation.
• Vegetation provides several important functions in
the performance of the landfill cover:
 Reduces erosion.
 Reduces precipitation infiltration.
 Enhances evapotranspiration, returning moisture
that has been absorbed into the topsoil layer to the
atmosphere to further reduce deeper infiltration.
18
 Lecture 8

Household Hazardous Waste

19
 Introduction
• Household Hazardous Waste (HHW) is a subgroup of
solid waste commonly found in MSW aswell as in
wastewater streams.
• USEPA definesHHW as theleftoverhousehold products
that contain;
• corrosive,
• toxic,
• ignitable, or
• reactive ingredients.
• Products, such as paints, cleaners, oils, batteries, and
pesticides, that contain potentially hazardous ingredients
require special care when you dispose of them.
20
 Improper disposal of HHW can include;
• Pouring down the drain,
• Spilling on the ground,
• Discharging into water bodies.
 The dangers of such disposal methods might
not be immediately obvious, but improper
disposal can pollute the environment and
pose a threat to human health.
21
  Special wastes sometimes categorized as HHW include;

• fluorescent lamps,
• computer components (CPU, monitors,
keyboards), televisions and other electronic
equipment.
 Electronics wastes are unusual HHW because
they often contain both valuable (silver and gold)
as well as very toxic(cadmium, lead, and other)
heavy metals.

22
 Reduction of HHW risks at home
• reducing the purchase of products that contain
hazardous ingredients.
• Using, storing, and disposing properly.
• Never store hazardous products in food containers.
• Never remove labels.
• Corroding containers require special handling.
• never mix the remaining HHW with other products
• follow the instructions for use and disposal

23
Reduction of HHW risks at home

24
  HHW Products that cause health effects are,

• Fertilizers and Pesticides

• oil-based paints,
• automotive products,
• drugs
• corrosive cleaners.
• cosmetics
 HHW Products that cause environmental effects are,
• Pesticides, fertilizers, automotive products, and
solvent-containing products.
• Video: http://www.youtube.com/watch?v=v4SztV63V-s&feature=related

25
 Health risks

• Source: Tchobanoglous & Kreith, 2002

26
 Health risks
• Indoor air pollution from HHPs is more of a threat
to human health than industrial pollution.
• Indoor air pollutants are of particular concern
because people spend most of their time indoors.
• Paints, home pesticides, air fresheners, perfumes
and charcoal create indoor air levels of toxic
substances higher than outdoor levels (U.S. EPA,
1993).
• Increase in asthma has been related to poor
indoor air quality (Dickey et al., 1995).
27
 Environmental risks
• The environmental risks of HHWs products
depend on:
 its solubility and mobility
 persistence and degradability
 toxicity level
 potential for penetrating land
• Chemicals that persist in the environment and
bio-accumulate in the food chain are of
particular concern.
28
 Environmental risks
• Hg, Pb and Cd build up in soils, water and
animals.
• Pesticides and fertilizers also leach into
groundwater and can result in pollution of
nearby water bodies and wells.

29
 Fire risks
• In the heat of a house fire HHPs may combine & react.
• Cans of gasolineo r kerosene or exploding aerosol cans
that have been heated and contain butane or toluene
may increase the intensity and spread-rate of the fire.
• Vaporized poisonous combustion products are a
significant threat to firefighters.

30
 HHW in wastewater
• HHPs are not only of concern in solid waste planning;
they also enter wastewater in a variety of ways.
• During use and disposal, HHP are washed down the
drain into water bodies.
• Local governments prohibit the discharge of HHW
(petroleum products, metals, acids or alkalis, paints,
solvents & pesticides) to storm water drains

31
Methods to decrease HHW effects
1. Product return: used to reuse or recyle products.
2. Disposal bans: encourage recyling of products.
3. Education: to increase society’s understanding .
4. HHW product collection methods: Arrange
programs to collect and dispose HHWs.
Video: http://
www.youtube.com/watch?v=rCc3SRraeFg&feature=rela
ted

32
 HHW product collection methods
1. HHW collection events method
• This collection method is arranged by one or a
few times yearly held at a central location for
few hours or days to collect HHW from local
citizens. Video: http://vimeo.com/41313332

33
2. Permanent facilities
• Permanent facilities collect HHW year-round.
• exchange areas are arranged for leftover paints,
solvents, pesticides, cleaning and automotive
products, and other materials.
• Therefore, HHW products can be used by
someone else, rather than being thrown away.
• Video: http://
www.youtube.com/watch?v=Pk-A6HbfLEM&feature=r
elated

34
3. Mobile collection

• Once or twice a year, a mobile system is

scheduled to visit small towns to collect HHWs.
4. Local business collection
• Certain HHWs may be dropped off at local
businesses for recycling or proper disposal.
• Some local garages, for example, may accept
used motor oil for recycling.

35
Lecture 9

Batteries

36
 1. Introduction
• Batteries are complex electrochemical devices,
composed of distinct cells, that generate electrical
energy from the chemical energy of their cell
components
• A battery cell consists primarily of a metallic anode
(negative electrode), a metallic oxide cathode (positive
electrode) and an electrolyte material that facilitates the
chemical reaction between the two electrodes.
• How do batteries work? Video: http://
www.youtube.com/watch?v=KkRwuM4S8BQ
37
 Classification of batteries

• According to their chemical componentsi,

batteries are classifies as wet, dry, primary and
secondary batteries
• In wet cell batteries, the electrolyte is a liquid.
• In dry cell batteries, the electrolyte is
contained in a paste, gel or other solid matrix
within the battery.

38
 Classification of batteries
• Primary batteries contain cells in which the chemical
reactions are irreversible, and they therefore can not
be recharged.
• In secondary batteries, the chemical reactions are
reversible and therefore can be recharged.

Types and Uses of Batteries

• Because of their different intended uses, consumer
batteries are usually distinguished as:
 automotive batteries (wet cells)
 household batteries( dry cells)
39
 Example of wet cell batteries
1. Lead-acid storage batteries
• These batteries are used in automobiles.
• consisting of lead electrodes in a liquid sulfuric acid
electrolyte.
• Its weighs ~16kg and lifetime is 3-4 years.
• In addition to lead, each battery contains;
• 4 Lof sulfuric acid,
• 1.5 kg of polypropylene plastic casing,
• 1.5 kg of polyvinyl chloride rubber separators, and
• 1.5 kg of various chemical sulfates and oxides to which the
lead is bound.
40
 dry cell batteries
• Dry cell batteries contain electrodes
composed of a variety of potentially
hazardous metals including Cd, Hg, Ni, Pb, Li
and Zn.
• In addition to electrodes and electrolytes,
batteries also contain other materials that are
added to control or contain the chemical
reactions within the battery.
• Common examples are household batteries.
41
Primary chemical components of
household batteries

42
 Environmental Impacts
• Used batteries Contain many potentially toxic
chemicals that can have adverse environmental and
human health impacts if discharged into water stream.
• Potentially toxic heavy metals that may be present in
batteries include Hg, Cd, Pb, Ag, Zn, Ni, Mn, Li, Cr, As.
% of toxic heavy metals in common household batteries

43
Collection of Used Batteries

• Used to recycle of their components.

• The collected used batteries are put separately.
Videos ;
http://www.youtube.com/watch?v=hPSICQztRm8
http://www.youtube.com/watch?v=14dW1chYAZc
http://www.youtube.com/watch?v=nCA6McK-Pz8
http://
www.youtube.com/watch?v=gGvmn6Aat5A&feature=related
44
 Recycling of automobile batteries

• Lead-acid batteries are recycled to recover the

Pb, sulfuric acid and polypropylene plastic
housing.
• The Pb is melted and extracted.
• The sulfuric acid can be recovered and used in
fertilizer.
• The plastic battery case can be recycled into
new cases or other recycledplastic products.

45
 Lecture 10

Waste Electrical and Electronic Equipment

(WEEE)

46
 Introduction
• WEEE refers to waste equipment that is
dependent on electric currents or
electromagnetic fields to work properly.
• In 2005,the volume of household WEEE was
estimated to be over 20 million tones globally.
• Due of their hazardous material contents,
WEEE may cause environmental problems if
not properly managed.

47
 Quantities of WEEE
• In EU:
Generation rate = 15 kg/ca.year
WEEE generated= 7.0 million tons (in 2005)
• In USA:
Generation rate = 22kg/ca.year
WEEE generated= 6.6 million tons (in 2005)
• In Japan:
Generation rate = 24kg/ca.year
WEEE generated= 3.1 million tons (in 2005)

C. Bastiaanet al. Int.J.Adv.Manufacturing Technol.47 (2010) 415-

436
48
 WEEE categories
1. Large household appliances: refrigerators, washing
machines, ovens, air conditioner.
2. Small household appliances: vacuum cleaners, irons,
grinders, coffee machines,
3. IT and telecommunications equipment: personal
computers, laptops, notepads, calculators, printers,
copying equipment, telephones.
4. Consumer equipment: televisions, radiosets, video
cameras
5.Lighting equipment: fluorescent lamps

49
6. Electrical and electronic tools: drills, saws, sewing
machines.

7. Toys, leisure and sports equipment: electric trains,

8. Medical devices: cardiology, dialysis,
9. Monitoring and control instruments: smoke
detectors, heating regulators, thermostats
10. Automatic dispensers: automatic dispensers
for hot or cold drinks

50
 Composition of WEEE

Composition of
WEEE for
Western Europe

51
 Major Hazardous Components 0f WEEE
• Batteries: A large proportion of heavy metals such
as lead, mercury, and cadmium are present in
batteries.
• Cathode ray tubes (CRTs): Pb in fluorescent
coating.
• Hg containing components: Hg is basically used in
medical equipment, data transmission, mobile
phones.
• Toner cartridges: May contain hazardous chemicals
that are moderately toxic if acute exposure occurs.
52
Major Hazardous Components 0f WEEE

• Printed Circuit Boards (PCBs): Cu, Pb and Cd

are common.
• Polychlorinated biphenyl: containing
capacitors: Have to be removed for safe
destruction.
• Plastics containing halogenated flame
retardants: During incineration they can
produce toxic components

53
 Material composition of WEEE
• WEEE are composed of
metals, particularly Cu, Al
and steel, attached to,
covered with or mixed
with various types of
plastics and ceramics.
• Cu and precious metals
make up more than 80%
of the value for most of
the WEEE.

54
Environmental İmpacts of WEEE

• Disposal of WEEE is of environmental concern

for a number of reasons.
 fate of dangerous materials in the waste,
 Depletion of resources and
 İmpacts of waste treatment methods.

55
 Dangerous materials

• WEEE contains a wide variety of dangerous

materials and components including:
 Printed circuit boards
 Flame retarded plastics
 Cathoderay tubes
 Liquid crystal displays
 Batteries
 Mercury switches
 Capacitors and resistors.
56
 Dangerous materials
 These components contain environmenty problematic
substances such as;
• Mercury (Hg), Lead (Pb), Cadmium (Cd), Chromium (Cr)
• CFC’s(chloro-fluoro carbons), PCB’s (polychlorinated
biphenyls), PCN’s(polychlorinated napthalenes),
Brominated flame retardants.
 These substances make up only a small proportion of
the total weight, but their potential environmental risks
are serious enough to warrant concern.

57
 Mercury (Hg)
• 22% of the annual world consumption of Hg is used in
electrical and electronic equipment (ENEA, 1995).
• Used for fluorescent tubes, and transforms the UV-light
created in the gas discharge to visible light.
• also used in medical equipment.
Cadmium (Cd)
• 99% of Cd is used in batteries.
• Used as a pigment and stabilizer in plastics.
• It is also used as a fluorescent material in screens

58
 Lead (Pb)

• the largest source of the Pb in consumer

electronics has been found to be contained in
CRT’s (Cathode Ray Tubes).
• CRT’s are found primarily in television sets and
computer monitors.
• television CRT contains 15-20% lead oxide.
Hexavalent Chromium Cr(VI)
• It is used as a corrosion protector for steel plates
and in printed circuit boards and plastic covers.

59
 Brominated Flame Retardants( BFR’s)
• Flame retardant plastics make up around 5.5%
of WEEE by weight or 25% of all plastic used in
EEE.
• BFR’s are designed into electronic products as
a means of ensuring flammability protection.
• They are mainly used in printed circuit boards,
components (connectors), plastic covers and
cables.

60
 Hierarchy in management of WEEE
• Options for the management of WEEE are reuse,
remanufacturing, recycling, incineration and
landfilling.
• Reuse: putting a material to the same or a
different use after it has fulfilled its original
function.
• Remanufacturing: is a production process in
which used products are disassembled, cleaned,
repaired, reassembled and qualified for new or
like-new equipments.
61
 Hierarchy in management of WEEE
• Recycling: is a process, wherein a used item is
turned in to a new product to reduce wastes.
• Incineration: is burning of the WEEE.
is the least favorable option.

62
 3 major steps of WEEE recycling

• Disassembly: separating hazardous and/or

valuable components for treatment.
• Upgrading: using mechanical and/or
metallurgical processing to up-grade desirable
materials content.
• Refining: recovered materials purified by using
chemical (metallurgical) processing so as to be
acceptable for their original use.

63