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SEMINAR ON

WET AIR OXIDATION


Prepared by: Neha B. Shinde.
(B.E Chemical)

INDEX
Chemical process industry(CPI)
Chemical engineering view
Process preview
Wet air oxidation
Oxidation reaction
Oxidizing power of common oxidizing
agents
Flow sheet of typical wet air oxidation
system
Process kinetics
Catalysts
Catalyst recovery
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Advantages & limitations

CHEMICAL PROCESS INDUSTRY ( CPI)


UTILITIES

RAW MATERIALS

GASEOUS WASTE

CPI

PRODUCTS, By PRODUCTS,

INTELLECTUAL

SOLID WASTE

INPUTS

LIQUID WASTE (~ 90 % of water in)

Chemical Engineers View


BIO PROCESSES
Aerobic
Anaerobic

PHYSICO CHEMICAL PROCESSES


1. SEPARATION

3. BULK MINERALIZATION

Liquid / Liquid Extraction

Incineration

Precipitation

Wet Air Oxidation

Adsorption
Membrane
2. REACTIVE DESTRUCTION
Hydro treatment

4. POLISHING PROCESS
Photo Chemical
Fenton
Sonication
Ozonation

Process Preview
BIO-PROCESSES
Most Popular Processes Operating At Near Atmospheric Pressure
And
Ambient Temperature.
Example : Bio Gas Generation From Spent Wash Of A Distillery Unit

Limitations:
Slow Rates, Large Volume. Hence, More Floor Area Reqd.
Often Need Engineered Micro-organisms
Do Not Permit, Invariably, Shock Loads, Toxic Wastes
Needs Elaborate Polishing Treatment For Water Recycle

Water Conservation Results In Concentrated Waste , Not Suitable For


Bio Process

OPTIONS AVAILABLE

INCINERATION
WET AIR OXIDATION

INCINERATION LIMITATIONS :
High Operating Cost.
High Capital Investment.
Water Can Not Be Recycled Unless Treated.

Wet air oxidation

MORE APPROPRIATELY : THERMAL PROCESS.

OXIDATION OF ORGANIC INTO INORGANIC SUBSTRATE IN


PRESENCE OF MOLECULAR O2 T = 100 _ 250 0C; Pressure:
O2 pressure 5 to 20 atm

O2 Solubility in water is minimum at near about 100oC.


Above 100 oC it is increasing with increase in temperature.

OXIDATION REACTION
FREE RADICAL MECHANISM
O2 + H2O

OH*

(via OH* radical formation)

NON SELECTIVE OXIDATION TO MINERALIZE OXIDIZABLE CONTAMINANTS


ORGANICS
O2
Ca

Hb

Nc

Pd

Xe

Sf

Og
H2O

C
N
H
P
X
S
O2

CO2
N2, NH3, NO3,
H2O
PO4
HX (halogen)
SO42O2

OXIDATION POWER OF COMMON


OXIDIZING AGENTS
RELATIVE TO OXYGEN
O2

1.00

Cl2

1.06

ClO2

1.06

HOCl

1.24

H2O2

1.48

O3

1.68

OH* (hydroxyl radical) 2.33


F2

2.50

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HIGHER OXIDATION POWER MEANS A RELATIVE LACK


OF SELECTIVITY.
This property IS USELESS for organic synthesis but
the MOST DESIRABLE in waste treatment.

WET

Oxidation

Technology

is

centered

around OH* radical as non-selective but


powerful oxidizing agent.

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STEAM

ENERGY RECOVERY
SYSTEM

OFFGAS

AIR COMPRESSOR
AIR
BFW
AIR
SATURATOR

WET OXIDATION
REACTOR
BFW

EFFLUENT

ENERGY RECOVERY
SYSTEM

TREATED
WATER

Typical Continuous Wet Oxidation System For Liquid Waste

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We have found that a lumped parameter series reaction in terms of COD


is more design friendly
k1
k2
(COD)
(COD)
Original
low mol. wt
Waste
intermediates

CO2 and H2O

In majority of cases, the second reaction step (k2) is the RATE LIMITING
STEP.
The kinetics is then given as

d(COD)
dt
m1;

k (COD)m (O2)n

n varies with 0.5 to 1.0

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CATALYSTS
Wet air oxidation reactions can be catalyzed by

homogeneous catalysts - compatible with MOC ,


easily recoverable, complete oxidation

Homogeneous catalysts could be recovered by


Precipitation
Ion exchange technique
Liquid emulsion membrane process

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Advantages and Limitations


Advantages

It can handle concentrated waste COD 10,000-500,000 mg/l

It can handle toxic chemicals cyanides, sulphides and priority


pollutants

Waste with high TDS can be handled

Energy integration possible

Very less space, even it can be underground.

Lower operating cost

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Limitations

Capital intensive due to exotic MOC.

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REFERENCES
www.edufive.com/
www.sci.com/
www.howstuffworks.com/

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Thank you

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