HAZARDOUS WASTE

TREATMENT
OUTLINE (Physical &
Chemical)

 Filtration & Separation

 Chemical Precipitation
 Solidification & Stabilization
 Chemical Oxidation & Reduction
 Pervaporation
 Ozonation
 Evaporation
Filtration & Separation
 Method of separation of fluid from solid
particles through the use of porous
medium
 Pressure gradient- driving force
 Pressure gradient – gravity, centrifugal
force, vacuum
Filtration & Separation
 Application
 Clarification
 Dewatering

 Clarification
 Slurry with less than 100 ppm of
suspended solids
 Depth filtration or cross-filtration
 Clear liquid water is removed for
discharge
Filtration & Separation
 Dewatering
 Slurry with 1 to 30% solids by weight
 Cake filtration

 Aim: concentrate solids into paste for

final disposal or further processing
Specific HW application of
Filtration
 Example 1- neutralization strong
acids with lime, followed by settling
and thickening of the resulting
precipitated solids as a slurry. The
slurry can be dewatered by cake
filtration and the effluent from the
settling step can be filtered by depth
filtration prior to discharge
Specific HW application of
Filtration
 Example 2- Precipitation of dissolved
heavy metals as hydroxides, carbonates,
or sulfides followed by settling and
thickening. Filtration application is similar
to Example 1
 Example 3- Treatment of oily
wastewaters by breaking of emulsions
followed by dissolved-air flotation. The
float is dewatered prior to incineration or
disposal
Specific HW application of
Filtration

 Example 4 – Destruction of toxic

organic compounds by biological
methods such as activated sludge.
The sludge is dewatered prior to
incineration
 Filtration vs S-L Separation
Processes
SOLID-LIQUID SEPARATION

BY DENSITY BY FILTRATION

CENTRIFUGATION DEEP BED SCREENING

FLOTATION GRAVITY
CAKE FILTRATION
SEDIMENTATION FILTRATION

CENTRIFUGE CROSSFLOW
DISSOLVED AIRTHICKENERS FILTER SCREENS
FLOTATION GRANULAR
VACUUM BED FILTERS
FILTERS
FILTER
PRESS
 CHEMICAL PRECIPITATION

 Process of converting soluble

substance into insoluble form
 Chemical reaction
 Changing the composition of the
solvent to decrease solubility of the
substance in it.
 Precipitated solids can be removed
by filtration or by settling
CHEMICAL PRECIPITATION

 Applications
 Water softening, removal of calcium
and magnesium ions
 In HW treatment, removal of toxic
metals from aqueous wastes
 Metals: arsenic, barium, cadmium,
chromium, copper, lead, mercury,
nickel, selenium, silver, thallium, zinc
CHEMICAL PRECIPITATION
 Major industries that may apply this
process
 Metal plating and polishing
 Steel

 Non-ferrous metals

 Inorganic pigments

 Mining

 Electronics
CHEMICAL PRECIPITATION
(SELECTED CHEMISTRY)
 Sulfide precipitation
M++ + FeS MS + Fe++

 Carbonate precipitation
Na2CO3 + M++ MCO3 + 2Na++

 Hydroxide precipitation
M++ + Ca(OH)2 M(OH)2 + Ca++
Lime vs. Caustic Precipitant
LIME
 Advantages
 Low chemical cost
 More settleable and
filterable precipitate
 Disadvantages
 More difficult to handle
than caustic
 Higher feed eqpt cost
 Higher maintenance
cost
 More sludge if high
sulfates are present
CAUSTIC
 Advantages
 More reactive
 Easy to handle
 Disadvantages
 High chemical cost
 Less settleable and
filterable precipitate
 Higher clarification and
dewatering cost
 Higher dissolved solids
in effluent
SOME EQUIPMENTS USED
SOLIDIFICATION &
STABILIZATION TECHNOLOGY
S/S refers to a generic set of
technologies that use binders and
additives
 Treat waste
 Remediating contaminated sites

 Decreases mobility and toxicity of the

contaminants in the waste
 Prepares the waste for final disposal
SOLIDIFCATION &
STABILIZATION TECHNOLOGY
 S/S converts the waste into solid
form and/or encapsulates the waste
constituents
 Monolithic form
 Granular form

 Claylike material
SOLIDIFCATION &
STABILIZATION TECHNOLOGY
 Solidification- a process in which
materials are added to the waste to
produce a solid
 Stabilization- process by which waste is
converted to a more chemically stable
form
 Chemical fixation- means solidification
and stabilization or the transformation of
the toxic compound into new, non-toxic
form
SOLIDIFCATION &
STABILIZATION TECHNOLOGY
 Encapsulation- process involving the complete
coating or jacketing of a waste particle or waste
agglomerate with a material such as the S/S
additive, binder, polymer, asphalt, or similar
material
 Vitrification- process wherby energy is applied to
a material to create a moltenlike state. High
temperature (1000oC) pyrolyzes and combust
the organics. It also stabilizes metals.
 Sorption- involves the addition of solid to take
up any free liquid in the waste.
 Activated carbon
 Anhydrous sodium silicate
 clay
Vitrification
AC Adsorption
SOLIDIFCATION &
STABILIZATION TECHNOLOGY
 Applications
 Radionuclides
 Municipal waste combustion residues

 Remediation of contaminated site

 Treating of heavy metals

 Controversial applications
• Halogenated organics PCBs
SOLIDIFCATION &
STABILIZATION TECHNOLOGY
 Advantages and disadvantages
depend on the following
 Process
 Binder

 The waste

 Site conditions

THE MERALCO EXPERIENCE

 CHEMICAL OXIDATION AND
REDUCTION
 Reaction in which the oxidation state of the
component atoms change as a result of the
transfer of electrons form one chemical species
to another
 A chemical specie is oxidized if it losses electrons
resulting to an increase in oxidation number
 Example: cyanide can be oxidized using chlorine
3Cl2 + 2OH- + CN- CNO- + Cl- + H2O
 Chlorine is the oxidant and it is reduced
 Cyanide is the reductant and it is oxidized
 OXIDATION OF
HAZARDOUS WASTES
 Organic wastes
 Phenols
 Indoles
 Pesticides
 Chlorinated solvents
 PAHs
 Benzene
 Toluene
 Inorganic contaminants
 Sulfides
 Ammonia
 Cyanide
 Heavy metals ( mercury, iron, manganese)
OXIDATION OF
HAZARDOUS WASTES
 Oxidation reagents
 Chlorine
 Chlorine dioxide

 Hydrogen peroxide

 Potassium permanganate

 Oxygen

 Ozone
Remediation of TCE
Contamination using Oxidation
Advanced Oxidation
Processes
 Involves the generation of highly reactive
intermediate, the hydroxyl radical or
(.OH) at ambient condition
 OH radical may be generated by
 Ozone/H2O2
 Ozone/UV
 Ozone/H2O2/UV
 H2O2/UV
 H2O2/Fe(II)
Reduction of Hazardous
Wastes
 Reduction has been used in conjunction
with precipitation for the removal of
heavy metals like chromium or copper
 Reductants used
 Sulfur dioxide
 Zero-valent metals
 Ferrous sulfate
 Sodium dithionate
 Hydrazine
 Sodium borohydride
IHI Selective Catalytic Reduction -Video
PERVAPORATION
 It is a membrane technology
 A process in which a liquid stream containing
two or more components is placed in contact
with one side of a nonporous polymeric
membrane
 A vacuum or gas purge is applied to the other
side
 The components of the stream sorb into the
membrane,permeate through the membrane,
and evaporate into the vapor phase
 Applications
 Removal of VOCs in water
PERVAPORATION
OZONATION
 Has been used for many years in
water disinfection
 Destruction of organic compounds,
bacteria, viruses, and many
parasites
 Odor control systems (H2S and
mercaptans)
OZONE GENERATOR IN AIR USING UV
Applications for IHW
 Aquaculture  Mining
 Breweries  Organic chemicals
 Biofouling control  Paints and varnishes
 Cooling towers  Petroleum refineries
 Cyanide and cyanates
 Phenols
 Electroplating
 Photoprocessing
 Food and kindred
products  Plastic and resins
 Hospitals  Pulp and paper
 Inorganic  Soaps and detergents
manufacturers  textiles
 Iron and steel
 Leather tanneries
Advantages & Disadvantages

ADVANTAGES DISADVANTAGES

 Generated on site  Higher capital cost

than other oxidant
 Air or oxygen
system
 Very strong oxidant  Will not degrade low
 Reacts with inorganics MW chlorinated
 Does not form organics
chlorinated compounds  Off-gas containing
 Temperature and pH ozone must be treated
less critical than with  Residual ozone
other oxidant essentially
 Treated effluents are nonexistent
oxygen-rich
THERMAL PROCESSES
FOR HW TREATMENT
 Incineration
 Wet Oxidation
 Supercritical water oxidation
 Plasma systems
 Pyrolysis
 HW Fuels in Industrial Processes
INCINERATION
 Proven technology for destruction of
hazardous wastes in solid, liquid and
gaseous form
 For HW Treatment, more commonly
used incinerator is Liquid-Injection
type.
 Other types are rotary kiln
incinerator, fluidized-bed
 1.Fluidized Bed
2.Calibrated Quartz sand
3.Air Supply
4.Gas Supply
5.Gas-Air Distributor
6.Pilot Burner
7.Direct Combustion
8.Post Combustion Chamber
9.Sludge Injection
10.Process Gases
11.Gas-Air Mixture
12.Secondary Air Supply
13.Exhaust off gases

FLUIDIZED BED INCINERATOR

 INCINERATION

 Operates from 1000oC to 1700oC

 Destruction efficiency is 99.99 per
cent of the principal hazardous
constituent
 99 per cent removal of hydrogen
chloride
 Stack emission does not to exceed
180 mg per dry standard cubic
meter
 INCINERATION Video lecture

 Applications in aqueous liquors

 Sodium glutamate phthalic anhydride
 Synthetic phenols phenol
 Polyester oil/water
 Agricultural-process wastes
 Applications in non-aqueous liquors
 Solvents waste oils
 Sludges halogenated hydrocarbons
 Organic acids
 Organometal components
 Aromatics
WET OXIDATION
 Aqueous phase oxidation process
 Organic and/or oxidizable inorganic
compound, dissolved or suspended in
water
 Mixing with oxygen (usually in air) at
temperature of 150-325oC.
 A gage pressure of 2060-20,690 kPa is
maintained
WET OXIDATION PLANT FOR
HAZARDOUS WASTES
 WET OXIDATION
TEMP RANGE, WASTE FUNCTION
oC TREATED

150-200 Sulfide Oxidation of WW and

containing WW improve dewaterability of
sludges
200-280 Specific Destruction of the compound
organic/inorga in WW; conversion of
nic pollutants refractory compounds to
biodegrable substances
280-325 Organic and Complete oxidation of
inorganic compounds in WW
compounds
SUPERCRITICAL WATER
OXIDATION
 Also known as supercritical wet oxidation
or hydrothermal oxidation
 Uses water above its critical temperature
and pressure
 Pressure is the medium for thermal
oxidation of organic compounds found in
HW
 HW – liquid or solid sludges
 Reaction temp- 400 to 600oC
SUPERCRITICAL WATER
OXIDATION
 Supercritical water
 Ideal medium for oxidation of organic wastes
 Critical T – 374oC; P- 22.1 MPa (3208 psia)
 At constant P, density of water decreases as
critical T is approached; hydrogen bonding
becomes weaker and solubility of water to
organic solvents becomes excellent
 Complete solubility of organics with
oxygen, combined with moderate reaction
temperature results to rapid oxidation of
organic compounds to CO2 and water
Products of SCWO of
Different Compounds
COMPOUND REACTION EFFLUENT pH
PRODUCT
Methylethyl H2O, CO2 Slightly acidic
ketone
trichloroethane H2O, CO2, HCl acidic

Dimethyl H2O, CO2, acidic

methylphosph H3PO4
ate
thiodiglycol H2O, CO2, acidic
H2SO4
amine H2O, CO2, N2 Slightly acidic

Cell mass H2O, CO2, N2 Slightly acidic

SCWO PILOT PLANT TESTING OF
ORGANIC WASTES(SELECTED)
FUNDING WASTE(S) TREATED
ORGANIZATION
A Inc Chlorinated organic
wastes; corrosive
wastewaters
US Army Smoke dye target
markers; tear gas
Kimberly Clark Pulp & paper process
wastes; disposable
diapers
German Co Metal-laden sludge from
glass grinding facility
Los Alamos National Process waste from
Labo plutonium
manufacturing
NASA Human metabolic
wastes
COMMERCIAL STATUS OF SWCO

 Eco-waste Technologies constructed a 5-

gpm facility at Huntsman Corporation’s
petroleum research and chemical
production facility in Austin, Texas, 1994
 Tubular reactor treats 4000 tons/year of WW
and concentrated organic wastes containing
methanol, polyols, amines, oxygenates, and
ammonia
 99.9% removal of TOC; 99.9% of waste
ammonia abd organic nitrogen converted into
N2
Destruction Efficiency for SCWO Pilot
Plant Treatability of U.S. Navy IHW
WASTE TUBULAR VESSEL
REEACTOR REACTOR
Organic based paint 99.955 % 99.995 %
sludge
Latex paint liquids 99.202 % 99.992 %
Adhesive sludge 99.952 % 99.994 %
Greases and lubricants 99.892 % 99.982 %
Mixed solvents 99.614 % 99.995 %
Nonchlorinated waste 99.998 % 99.993 %
oil
Chlorinated waste oil 99.969 % 99.994 %
AFFF solution 99.998 % 99.995 %
Triethanol amine 99.941 % 99.993 %
Waste mixture 99.995 % 99.996 %
PLASMA TECHNOLOGY

 Uses plasma-arc device to produce

extremely high temperature (approx.
10,000oC)
 Destroys highly toxic wastes
 For liquid waste destruction and for solid
waste destruction
 Successfully applied in the metals
industry
 For HW treatment, it is still in pilot-scale
research stage
 Promising for dioxin containing sludge
PLASMA SCIENCE &
TECHNOLOGY
http://www.plasmas.org/
PLASMA TECHNOLOGY
 Plasma generation
 Electrical discharge through a gas
 In passing through a gas, electrical
energy is converted to thermal energy
 The thermal energy is absorbed by the
gas molecules which are activated into
ionized atomic state,losing their electrons
 Radiation is emitted when molecules or
atoms relax from highly activated state to
lower energy levels
PLASMA TECHNOLOGY
 Research has been conducted on
various types of wastes including
infectious medical wastes
 The products of the wastes after
treatment are environmentally
friendly
 Non-leachable glassy slag
 Off-gas that can be used as fuel
PYROLYSIS
 This is thermal degradation of
organic species in the absence of
oxygen or other reactant gases
 Degradation of organic compounds
gives product mix of gases (CO, H2,
etc), condensable liquids (oils and
tars), and solid residue (chars and
inorganics)
PYROLYSIS Applications to HW

 Applied to neat liquid like spent

solvents and heterogeneous solid
matrix like sludge and contaminated
soils
 HW containing halogenated
hydrocarbons
Advantages of PYROLYSIS
 Takes place at 400-800oC, lower than
incineration temperature
 It is endothermic making it possible to control
reaction by regulating the heat addition
 Fly-ash formation is lower than incineration
 Heavy metal volatilization and emissions are
greatly reduced
 Less CO2 formed
 Caustic can be added during pyrolysis of
halogenated wastes to trap halogens
HAZARDOUS WASTES AS FUEL
IN INDUSTRIAL PLANTS

 High temperature industrial

processes for destruction of HW
 Industrial boilers
 Cement kilns
 Asphalt plants
 Blast furnace
 Glass making furnace
CANDIDATE INDUSTRIAL PROCESSES
FOR HW INCINERATION

PROCESS PROCESS GAS RES.

TEMP, oC TIME, S
Lime kiln 1093 8
Aggregate kiln 1093 2
Asphalt plant dryer 427 2
Iron & steel blast 1870 1
furnace
Brick tunnel kiln 1200 4
Glass furnace 1260 4
Copper reverberatory 1426 2
furnace
Lead blast furnace 1200 6
HW UNDESIRABLE FOR
INCINERATION IN INDUSTRIAL
PROCESSES

 Organic cyanides
 PCBs
 Insecticides
 Pesticides
 Radioactive materials
BIOLOGICAL PROCESSES

 CONVENTIONAL FOR WASTEWATER

TREATMENT
 EMERGING BIOPROCESS
 COMPOSTING
 Phytoremediation
CONVENTIONAL BIOLOGICAL
PROCESSES FOR WASTEWATER
TREATMENT
 Aerobic
 Suspended growth
 Activated sludge
 Fixed film

 Anaerobic
 Fixed film
• Filter
• Fluidized bed
• Upflow anaerobic sludge blanket
EMERGING
BIOPROCESSES
 Biological processes can be used for
remediating contaminated
groundwater, sludges and soil
 Low cost
 Less safety and health concerns
 Ex-situ vs in-situ bioremediation
Enhancements used in
Bioremediation
 Moisture
 Oxygen in air/hydrogen peroxide
 Nutrients like phosphorus and trace
minerals
 Surfactants, biosurfactants, and/or
dispersants to enhance bioavailability of
the hydrocarbons
 Bioaugmentation with specialized
microbial cultures assumed to be effective
in enhancing biodegradation of HC
contaminants
Simplified Bioremediation
Process (Hydrocarbons)

Carbon
Dioxide
Chlorinated
Hydrocarbons Bacteria

Water

Enzymes (Aid in breakdown

of petroleum products)
Phytoremediation
 plants are used to degrade or
transform contaminants
COMPOSTING HW
TREATMENT
 Favorable for the land treatment of
recalcitrant wastes
 For the treatment of organic
compounds
 Useful in the isolation of organisms
for the biotreatment

BIOFILTER FOR VOC AND

ODOR CONTROL