CIVE 4310 NURAZIM IBRAHIM, PHD.

HAZARDOUS WASTE CIVIL ENGINEERING PROGRAMME

FACULTY OF ENGINEERING &
SCIENCE TECHNOLOGY, IUKL
 Water; water, every where,
And all the boards did shrink;
Water; water, every where,
Nor any drop to drink
Coleridge
Hazardous Waste Treatment
HAZARDOUS WASTE MANAGEMENT SYSTEM

PRIORITY

Figure 1: RCRA’s Cradle-to-Grave Hazardous Waste Management System:

A comprehensive regulatory program to ensure that hazardous waste is managed
safely from “cradle to grave” meaning from the time it is created, while it is
transported, treated, and stored, and until it is disposed.
Introduction

• Based on the Resource Conservation and Recovery Act (RCRA),

treatment and disposal is the “final link in the cradle-to-grave
hazardous waste management system.”

• Treatment, storage, and disposal practice involves a large variety of

units and technologies. Thus, the TSD regulations are far more
extensive than for generators and transporters.

• It is encouraged for you to explore the technical literature and the

RCRA Subtitle C regulations for details.
Administrative and Nontechnical Requirements

• The administrative and nontechnical requirements are intended to

ensure that owners and operators establish the necessary procedures
and plans to operate the TSD facility according to established practice
and to handle any emergencies or accidents.

• The administrative and nontechnical requirements for interim status

and permitted TSDFs are very similar. These requirements are found in
Subparts A through E of 40 CFR Parts 264 and 265.
Administrative and Nontechnical Requirements

Subpart A — Facilities That Are Subject to the Regulations

• In general, all owners or operators of facilities engaged in the
treatment, storage, or disposal of hazardous wastes must comply with
the 40 CFR 264/265 regulations unless they are specifically excluded.

Subpart B — General Facility Standards

• All facilities handling hazardous wastes must obtain an EPA
identification number.
• Owners and operators of TSDFs must ensure that the wastes being
handled are correctly identified and managed according to the
regulations.
• They must ensure that facilities are secure and are operating properly.
• Personnel working in the facilities must be trained to perform their
duties correctly, safely, and in compliance with all applicable laws,
regulations, and codes.
Administrative and Nontechnical Requirements

Subpart C — Preparedness and Prevention

• Facilities must be designed, constructed, maintained, and operated to
minimize the possibility of a fire, explosion, or any unplanned sudden or
nonsudden release of hazardous waste or hazardous waste
constituents which could threaten human health or the environment.

Subpart D — Contingency Plan and Emergency Procedures

• A contingency plan must be in effect at each TSD facility
• The plan must be designed to minimize hazards to human health or the
environment from fires, explosions, or any release of hazardous waste
constituents.
• The plan must be implemented immediately whenever there is a fire,
explosion, or release which could threaten human health or the
environment.
Administrative and Nontechnical Requirements
Subpart E — Manifest System, Record Keeping, and Reporting

• The TSDF owner or operator receiving the waste is responsible for ensuring that the
waste described on the manifest is the same as the waste on the truck.
• The intent is to ensure that there are no significant discrepancies in the amount (e.g.,
an extra drum) or type of waste (e.g., acid waste instead of paint sludge) that was
shipped by the generator.
• If a significant discrepancy is discovered, the TSDF must reconcile the difference with
the generator or transporter.
• If the difference cannot be cleared up, the EPA must be notified within 15 days of the
incident.
• The owner or operator or his agent must sign and date all copies of the manifest to
verify that the waste has reached the designated facility.
• The copy of the signed manifest must be placed in the TSDF files, and a copy must be
sent to the generator within 30 days.
• If it is necessary to send the waste to another facility, the owner/ operator/ agent must
initiate a new manifest.
• Subpart E includes extensive record keeping and reporting requirements (EPA 1998,
Section III).
General Technical Standards for Interim Status
and Permitted Facilities

Part 265, Subpart F — Groundwater Monitoring

• Owners and operators of surface impoundments, landfills, and land

treatment facilities used to manage hazardous waste must meet
minimum groundwater monitoring requirements.
• The interim status facility requirements in 40 CFR 265.91 call for a
monitoring system consisting of at least one well upgradient from the
facility and three downgradient wells.
• The upgradient well(s) must provide data on groundwater that is not
influenced by leakage from the waste management unit.
• The downgradient wells must be placed to intercept any waste migrating
from the unit should a release occur.
 General Technical Standards for Interim Status
and Permitted Facilities
Figure 2: Groundwater monitoring well layout for a
landfill disposal facility.
(Adapted from Glenn R. Smart and David K. Cook,
RCRA and CERCLA Groundwater Well Locations and
Sampling Requirements, Hazardous Materials Control,
1(3), May/June 1988.)
Figure 3: Natural drawdown interference with
groundwater monitoring regime.
(Adapted from Glenn R. Smart and David K. Cook,
RCRA and CERCLA Groundwater Well Locations and
Sampling Requirements, Hazardous Materials Control,
1(3), May/June 1988.)
General Technical Standards for Interim Status
and Permitted Facilities
Part 264, Subpart F — Releases from Solid Waste Management Units

• Facilities with permitted landfills, surface impoundments, waste piles, or

land treatment units must conduct groundwater monitoring to detect,
characterize, and respond to releases of hazardous wastes or hazardous
waste constituents into the uppermost aquifer.
• Part 264, Subpart F, goes beyond compliance monitoring and establishes
a three-stage program designed to detect and remediate any releases
from regulated units:
1. Detection monitoring — to detect releases at a compliance point
2. Compliance monitoring — once a release has been detected to
determine if the Groundwater Protection Standard (GWPS) has been
exceeded
3. Corrective action — to remediate a release to the uppermost aquifer
General Technical Standards for Interim Status
and Permitted Facilities
Subpart G — Closure, Post-Closure

• Closure is the period when wastes are no longer accepted, during which
all waste processing must be completed, and a final cap or cover is
applied to the land treatment facility.
• The closure rules are intended to preclude future releases of hazardous
wastes, waste constituents, or decomposition products of hazardous
wastes.
• All equipment, structures, and soil must be removed, disposed of, or
decontaminated.
• The closure and post-closure standards consist of two parts: (1) the
general standards in 40 CFR Parts 264 and 265, Subpart G and (2)
technical standards for specific types of hazardous waste management
units as detailed in Parts 264 and 265, Subparts I through X.
General Technical Standards for Interim Status
and Permitted Facilities

Subpart H — Financial Requirements

• RCRA originally established financial requirements to assure that funds

would be available to pay for closing a facility, for rendering post-closure
care at disposal facilities, and to compensate third parties for bodily
injury and property damage caused by accidents related to the operation
of a TSDF.
Hazardous Waste Treatment
• Since, Industrial Revolution in 18th century, the use of chemicals have
been spreading more and more.
• More than 73 million organic and inorganic substances identified by
CAS (Chemical Abstracts Service) number and over 100,000 different
substances in use.
• Notwithstanding the importance of chemicals in enhancing quality of
everyday life, it is well-known that they also have the potential to
adversely impact human health and the environment if not managed
properly.
• Impacts:
• health related effects range from acute poisoning to long term
effects (e.g. cancers) – consumption of contaminated drinking water
and food
• effects on ecosystems –inhalation of polluted air/direct skin contact
• stratospheric ozone depletion (due to chlorofluorocarbons)
• oceans pollution – fish contaminated
Hazardous Waste Treatment

• Chemical consumption in developing countries is likewise

growing much faster than in developed countries and could
account for a third of global consumption by 2020 (Cavallini
et al., 2014).
• There is a potential connection between lack of knowledge of
proper chemicals management and risks of exposure to toxic
and hazardous chemicals.
• The main approach of hazardous waste treatment is 3R
(reduce, recover and reuse).
• It aims not to eliminate, which is virtually impossible, but to
greatly decrease the total amount of chemical
hazardous waste, by means of correct practices,
preventing the ultimate disposal of hazardous waste
Hazardous Waste Treatment

• E.g. if a toxic solvent is needed for a generic chemical

synthesis, care should be taken in order not to exceed
maximum amount requested and final distillation could be
carried out for recovery and re-use purpose.

• Advantages:
• less hazardous waste, means
• less disposal cost
• less purchase of new chemicals(whether recovery and
reuse is possible)
• Less potential hazard for the facility’s workers involved in
waste management.
 Hazardous Waste Treatment
• Hazardous waste treatment innovation is being driven by the need
for effective and economical processes for reclaiming, treating, or
destroying wastes rather than landfilling them without treatment

• Hazardous Waste Management Options and Priorities is showed

below

Source Secure
Separation Exchange /
Reduction Energy Ultimate
(Volume Sale as Raw Treatment
(Process Recovery Disposal
Reduction) Materials
modification) (Landfill)
Hazardous Waste Treatment
• Hazardous waste treatment is a rapidly developing industry full of
experimentation and innovation.
• This innovation is being driven by the need for effective and economical
processes for reclaiming, treating, or destroying wastes rather than
landfilling them without treatment.
Subpart Q — Chemical, Physical, and Biological
Treatment

• A list of some of the chemical, physical, and biological treatment

processes which are regulated by 40 CFR 265, Subpart Q, is provided in
the next slide.
• There are a several treatment processes that are rarely use in treatment
of RCRA waste which include
• Distillation,
• Reverse osmosis,
• Ion exchange, and
• Filtration
• The processes are frequently waste-specific, therefore, the EPA has not
developed detailed regulations for any particular type of process or
equipment. Instead, general requirements have been established in Part
265, Subpart Q, to assure safe containment of hazardous wastes.
Subpart Q — Chemical, Physical, and Biological
Treatment
• The Subpart Q general requirements require owners/operators to:
• Avoid treating any waste that could cause equipment to rupture, leak,
corrode, or otherwise fail.
• Equip continuous waste feed conveyances with a feed cut-off system.
• Comply with special requirements for ignitable or reactive wastes.
• Remove any waste characteristic before placing the waste in the
process or equipment.
• Comply with special requirements for waste analyses in addition to
general waste analysis requirements.
• Inspect discharge control, safety equipment, and monitoring data at
least daily.
• Inspect construction materials of the treatment process for corrosion,
leakage or erosion at least weekly.
• Remove all hazardous waste and residues from processes, equipment,
and discharge confinement structures at closure (40 CFR 265.401-
404).
Hazardous Waste Treatment, Recovery, and Disposal
Processes: 1) Physical Treatment Processes
b) Liquid Solid Separation
a) Gas cleaning
1. Centrifugation 7. Foaming
1. Mechanical collection 2. Clarification 8.
2. Electrostatic precipitation Sedimentation
3. Fabric filter 3. Coagulation 9. Thickening
4. Wet Scrubbing 4. Filtration
5. Activated carbon adsorption 5. Flocculation
6. Adsorption 6. Floatation

c) Removal of specific components

1. Adsorption 7. Leaching
2. Crystallization 8. Reverse osmosis
3. Dialysis 9. Stripping
4. Distillation 10. Solvent extraction
5. Electrodialysis
6. Evaporation
Hazardous Waste Treatment, Recovery, and Disposal
Processes

2) Chemical treatment
3) Biological treatment
processes
processes
1. Absorption
1. Aerobic systems
2. Chemical oxidation
2. Anaerobic systems
3. Chemical precipitation
3. Activated sludge
4. Chemical reduction
4. Spray irrigation
5. Wed oxidation
5. Tricking filters
6. Ion exchange
6. Waste stabilization ponds
7. Neutralization
7. Rotating bio contactors
8. Chemical fixation and
solidification
9. Dehalogenation
Hazardous Waste Treatment, Recovery, and Disposal
Processes
4) Thermal treatment
processes

1. Incineration
2. Pyrolysis
3. Vitrification

5) Ultimate disposal processes

1. Deep-well disposal
2. Dilution and dispersal
3. Ocean dumping
4. Sanitary landfill
5. Land burial
Figure 4: Treatment and disposal alternatives for industrial wastes (Adapted
from Hazardous Waste Management, © 1989, McGraw-Hill, New York.)
MALAYSIA HAZARDOUS WASTE MANAGEMENT SYSTEM
• In Malaysia, Kualiti Alam had
established the centralized integrated
scheduled waste management centre
• They are responsible for waste
collection, transportation, treatment,
and final disposal of hazardous
wastes
• Multiple technologies are used in the
treatment and disposal depending on
types of scheduled wastes which
comprise
• incineration plants,
• physical and chemical treatment
plants,
• solidification treatment plants,
• secure landfills and
• clinical waste treatment centres.

Overview of Hazardous Waste Management Status in Malaysia

Introduction: Physical Treatment
• The schematic of Figure 1 (PREVIOUS SLIDE) aligns types or
categories of industrial wastes with the treatment processes and
ultimate disposal usually applied.

• The volume of a waste destined for treatment or disposal

can often be reduced by physical processes such as:

Solvent Stripping
extraction Evaporation

Adsorption Centrifugation Clarification

Activated Carbon Adsorption
• Activated carbon is an example of carbonaceous adsorbent
produced from thermal decomposition and activation of carbon rich
materials such as wood, wood charcoal, bituminous coal, coconut
shells and sawdust.

• Activated carbon adsorption employ to simultaneously removed

organic (low molecular weight substances) and in-organic
dissolved substances (e.g. metals and chlorinated compounds)
adsorption of the chemical substances onto a carbon matrix.

• Activated carbon, resins, solid hydroxides or oxides and synthetic

zeolites are common engineered adsorbent which can be found in
today markets. Natural adsorbents include coal, plant materials,
and even sewage sludge.
 Activated Carbon Adsorption

• Activated carbon is known as a powerful

adsorbent since it is capable to remove
various pollutants from inorganic to
organic pollutants

• Characteristics of Activated carbon:

• Large surface area (600 – 1000 m2/g)
• Non-polar surface
• Posses specific structure (e.g.
honeycomb structure as shown in the
figure) and micro pores resulting in
high internal surface area and micro-
pore volume

Activated carbon from palm bio-waste

 Activated Carbon Adsorption

• Typically use in the form of powder or

granular depending on the application
and process
• Adsorption behaviours show by activated
carbon (Worch, 2012):
• The capacity uptake increases with
increasing of pore volume
• Organic substances adsorption is
higher with lower adsorbate polarity
• Nowadays, there are several composite
media is developed as an alternative to
activated carbon (e.g. activated carbon
zeolite composite)
Carbon adsorption pressurized contractor
 Activated Carbon Regeneration

• The used carbon is regenerated in

ovens or by passing live steam through
the carbon.
• Figure on the right side show a carbon
regeneration system is diagrammed

Carbon regeneration system

 Stripping
• Air and steam stripping is include as one of the
physical treatment because of strippers have
been employed in so many of the early site
remediation efforts.
• Stripping is most frequently used to remove
volatile organics from wastewaters or
contaminated groundwater
• Strippers generally involve towers containing
cascades, trays, or manufactured media, with
induced-draft air or live steam passing upward
and contaminated water cascading or trickling
downward over optimized surface areas.
• A counter-current packed-tower air stripper is
diagrammed in Figure. Steam stripping towers
operate on a similar principle with live steam
injected directly into the liquid waste.
Counter-current packed tower stripper.
Stripping
• In theory, the gas-liquid system reaches an equilibrium, based upon
Henry’s law.

‘Henry Law’
At constant temperature, the weight of gas absorbed by a given volume of
a liquid is proportional to the pressure at which the gas is supplied, e.g., if
a liter of water dissolves 5 g of a gas under 1 atm of pressure, it will
dissolve 10 g of the same gas under 2 atm of pressure

• The volatile contaminants are preferentially removed and are carried out
as a vapor with the exhaust air stream or the spent steam through the
top of the unit.

• Further treatment (carbon adsorption, incineration) must be applied to

the exhaust vapors in order to capture and/or destroy the separated
volatiles
Stripping
• In theory, the gas-liquid system reaches an equilibrium, based upon
Henry’s law.

‘Henry Law’
At constant temperature, the weight of gas absorbed by a given volume of
a liquid is proportional to the pressure at which the gas is supplied, e.g., if
a liter of water dissolves 5 g of a gas under 1 atm of pressure, it will
dissolve 10 g of the same gas under 2 atm of pressure

• The volatile contaminants are preferentially removed and are carried out
as a vapor with the exhaust air stream or the spent steam through the
top of the unit.

• Further treatment (carbon adsorption, incineration) must be applied to

the exhaust vapors in order to capture and/or destroy the separated
volatiles
 Physical Treatment

Figure 2. Centrifuge Figure 3. Gravity separation

cones.

1. Both processes make use of differences in specific gravity or mass

to separate harmless or nonhazardous components from the
hazardous components.
Introduction: Chemical Treatment
• Used to alter chemical properties of wastes in order to facilitate or
enable further treatment; to render the wastes nontoxic/non-
hazardous for disposal; or to solidify or stabilize the wastes for
ease of handling or reduced leachability or to render them non-
degradable.

• The general categories of chemical treatment include:

Acid/base Chemical
precipitation Oxidation/redu
neutralization
ction (redox)

Chemical
Solidification
Electrolysis Hydrolysis extraction &
/ Stabilization
Leaching
Introduction

• E.g. if a toxic solvent is needed for a generic chemical

synthesis, care should be taken in order not to exceed
maximum amount requested and final distillation could be
carried out for recovery and re-use purpose.

• Advantages:
• less hazardous waste, means
• less disposal cost
• less purchase of new chemicals(whether recovery and
reuse is possible)
• Less potential hazard for the facility’s workers involved in
waste management.
Neutralization

• Widely used chemical process in which the pH of an acidic,

corrosive, or caustic wastewater or gas is adjusted to a more
neutral range

• Applied as pre-treatment step or final treatment process

• Methods of neutralizing acids wastes include

• Adding appropriate amounts of strong or weak base to
the waste
• Passing acidic waste through limestone beds
• Mixing acidic waste with lime or dolomite lime slurries
• Mixing the acidic waste with a compatible alkaline waste
Neutralization

• Methods of neutralizing alkaline wastes include

• Adding appropriate amounts of strong or weak acid to the
waste
• Adding compressed carbon dioxide gas to the waste
• Blowing flue gas through the waste
• Mixing the alkaline waste with a compatible acidic waste
Precipitation
• If the solubility product of a metal hydroxide is suitable for
precipitation, sodium hydroxide (caustic soda) or calcium
hydroxide (lime slurry) can be used to treat liquid wastes
containing heavy metals.
• The addition of a hydroxide ion precipitates the metals:
M+2 + 2(OH–) → M(OH)2
• The coagulation of the precipitated metals is both a physical
and chemical process.
• The attraction of cations for anions causes the formation of a
floc
• It is frequently necessary to add a coagulant or flocculant to
aid in separation of the precipitant from the remaining
soluble phase
Precipitation

• The mild turbulence in the stirred tank causes the small

particles to collide forming a sludge with a concentration of
20 to 50% solids
• This process must then be followed by solidification or other
processes specific to the sludge formed, in order to render
the sludge harmless to the environment.
• Calcium hydroxide and sodium hydroxide are used by many
industries to precipitate heavy metals; however, precipitation
of chromium requires that all hexavalent chrome-containing
ions be reduced to the trivalent state, since hexavalent
chromium cannot be removed directly by hydroxide
precipitation.
Precipitation
 

• Using sulfurous acid as a reducing agent:

Green Precipitate
Chemical Treatment

A typical processes in which an in-organic acid is used as a reducing agent neutralization,

precipitation, and chemical oxidation/reduction
Stabilization and Solidification

• Stabilization and solidification of liquid and semi-solid wastes

are processes used to immobilize the hazardous constituents
and provide physical structure to a waste, in order that it can
be easily handled and land-disposed with minimized hazard
to the land and groundwater.
• The processes that are used may involve some chemical
reactions, but are primarily used to dewater and/or achieve
physical encapsulation of the constituents.
• Metals and nonmetals can be solidified with pozzolan (e.g. an
additive such as siliceous volcanic ash or fly ash to improve
the curing and strength properties of Portland cement
concrete) and lime after the waste has been precipitated.
Stabilization and Solidification

• A typical formulation is
Final Solid = Lime + Fly Ash + Waste + Water

• where lime is 5 to 15% by weight, fly ash is 50 to 65% by

weight, waste is 8 to 19% by weight, and water is 10 to 60%
of the original sludge by weight.

• For an organic sludge, a typical mixture ratio would be as

above except having water at 10 to 20% by weight
Solidification process

Spread mixed
Liquid waste Lime & fly ash
Mixing in a matrix in
storage and storage and
pugmill drying beds to
blending dispensing
be solidifies
Stabilization and Solidification

• Solidification and/or stabilization technologies that may be

suitable for specific situations include
• Thermoplastic materials such as bitumen, asphalt,
polyethylene, or polypropylene
• Thermosetting reactive polymers including reactive
monomers urea-formaldehyde, phenolics, polyesters,
epoxides, and vinyls, which form a polymerized material
when mixed with a catalyst
• Polymerization of spills of chemicals that are monomers or
low-order polymers by adding a catalyst
Oxidation and Reduction

• oxidation and reduction can be used to render hazardous

wastes less hazardous or harmless.
• An oxidation reaction increases the valence of an ion with a
loss of electrons.
• A reducing reaction decreases the valence with a gain of
electrons.
• Reactions that involve both oxidation and reduction are
known as redox reactions.
Oxidation and Reduction
 
• Cyanide-bearing wastewater, commonly generated by the
metal-finishing industry, is typically oxidized with alkaline
chlorine or hypochlorite solutions (the chlorine is reduced)
• The cyanide (the contaminant of interest) is initially oxidized
to a less toxic cyanate and then to carbon dioxide and
nitrogen in the following reactions:

• Oxidation of cyanide may also be accomplished with

hydrogen peroxide, ozone, and electrolysis
THE END