Unit-5

Adsorption and Oxidation Processes

Chemical Process:
 Waste water treatment is any operation / process or combinations of operations and processes that can
reduce the objectionable properties of waste water and render it less dangerous.
 Waste water treatment is a combination of physical, chemical and biological processes.
 Methods of treatment in which application of physical forces predominate, are known as unit
operations.
 Methods of treatment in which chemical or biological activities are involved, known as unit
processes.

Miscellaneous Treatment Processes:

(A) Aeration
(B) Removal of iron and manganese
(C) Removal of colour odour and taste
A. Aeration:
 Aeration is the process of bringing water and air into close contact in order to remove dissolved
gases, such as carbon dioxide, and to oxidize dissolved metals such as iron.
 It can also be used to remove volatile organic chemicals (VOC) in the water.
 Aeration is often the first major process at the treatment plant. During aeration, constituents are
removed or modified before they can interfere with the treatment processes
Purpose of aeration:
1. To make water fresh by absorbing oxygen from air.
2. To release dissolved gases (CO2, H2S etc) to atmosphere.
3. To remove bad taste and odour.
4. To reduce corrosiveness of water.
5. To precipitate Fe and Mn to some extent by oxidizing.
6. To kill harmful bacteria to some extent.
7. To mixing chemicals to water.
Chemical substances affected by Aeration
• Volatile organic chemicals, such as benzene, found in gasoline, or trichloroethylene, dichloroethylene
• Carbon dioxide
• Hydrogen sulfide (rotten-egg odor)
• Methane (flammable)
• Iron (will stain clothes and fixtures)
• Manganese (black stains)
• Various chemicals causing taste and odor
B. Removal of iron and manganese:
Effect:
i. Produce taste, odour and brown red colour.
ii. Stains on clothes, corrosion and clogging accumulation of precipates.
iii. Causes difficult in various industrial process.
Methods:
(a) By aeration
(b)By adding lime
(c) Passing over manganese zeolite
C. Removal of colour odour and taste:
Purpose: Removal of colour, odour and taste
Methods:
(a) By aeration
(b)By activated carbon treatment
• Activated carbon is manufactured by heating saw dust, paper mill waste etc. at 500°C in a closed
vessel in controlled condition of burning at 800°C.
• readily available in market in powder or granular form
• Absorbs organic matters and removes colour, odour and taste.
(c) Using copper sulphate: in swimming pools

Chemical Oxidation:
 The objective of chemical oxidation in water and wastewater treatment is to transform undesirable
chemical constituents to a more oxidized state which reduces the pollution potential.
 Use of Ozone (O3), Hydrogen peroxide (H2O2), Permanganate (MnO4), Chloride dioxide (ClO2),
Chlorine (Cl2) or (HOCl), and Oxygen (O2)
 To reduce /degrade BOD, COD, ammonia, non-biodegradable organic compounds.
 It is often unnecessary to carry the oxidation of a compound to completion since, depending on the
oxidant and oxidizing conditions, the intermediate oxidation products which may be formed will be
of much lower toxicity or less objectionable characteristic than the original materials.
 Complete oxidation may not only be impractible from a treatment standpoint, but also represents a
non-justified economical outlay.
 Subsequently, chemical oxidation might be considered as a selective modification or elimination of
objectionable or toxic substances, including :
 Inorganic constituents, such as Mn(II), Fe(II), S2-, CN-, SO32-
 Organic compounds, such as phenols, amines, humic acids, other taste, odor, or color producing or
toxic compounds, bacteria and algae
Advanced oxidation process:

1. Ozone water treatment (Ozonation):

 Ozone water treatment is the process of using ozone to purify water that is removing microorganisms
that can make you sick from drinking water.
 This process has been used in drinking water plants since 1903 where the first industrial Ozonation
plant was built.
Process:
Ozone will initiate a series of reactions in water that are very complex and quite specific to the water
being treated.
Ozone directly reacts with water via three mechanisms:-
(1)Cycloaddition (+&-); on unsaturated bonds as a dipole.
(2)Electrophilic (+); on molecular sites with strong electronic density
(3)Nucleophilic (-); on molecular sites with an electronic deficit.
Advantages
 Ozone is very effective and rapidly reacts with bacteria viruses and has stronger germicidal properties
than chlorination.
 It has a very strong oxidizing power with a short reaction time.
 The treatment process does not add any chemicals to water.
 Ozone can eliminate a wide variety of inorganic, organic and microbiological problems and taste and
odour problems.
Disadvantages
 Ozone water treatment is much expensive than other treatment levels.
 In ozone water treatment there must be professional proficient for water treatment and system
maintenance.
 It does not provide any germicidal or disinfection residual to prevent re growth.
 Due to its less solubility in water special mixing techniques are needed.
 Fire hazards and toxicity issues associated with ozone generation.

2. Photochemical Oxidation Processes:

Photochemical Processes Wavelength
UV (photolysis) < 190 nm
H2O2/UV < 300 nm
O3/UV < 320 nm
O3/H2O2/UV < 320 nm
TiO2/UV (photocatalysis) < 400 nm
Fe+2/H2O2/UV (photoFenton) < 550 nm
Fe+2/e-/UV (photoelectroFenton) < 550 nm

1. H2O2 PHOTOLYSIS:
O-O bond strength in H2O: ca. 213 kJ mol-1
(corresponding wavelength = 560 nm)
 H2O2 + hν → 2 °OH
pKa = 11.6
HO2- + hν → °OH + O°-O°- + H2O → °OH + OH-ε254
H2O L mol-1 cm-1
HO L mol-1 cm-1
Advantages
• no residues
• H2O2 is miscible with H2O
• H2O2 is readily available, transportable, storable
Drawbacks
• handling/safety precautions
• very weak absorption except at high pH (several tens of kW-lamps) ; inner filter effect by organics
• needs UVC (254 nm). Germicidal
• °OH scavenging by H2O2 (°OH + H2O2 → HO2° + H2O)
2. Fentons method:
⊙AOP (advanced oxidation processes): generating OH
→ Fenton’s reagent: H2O2 / Fe2+
→ Fenton-like reagent: H2O2 / Fe3+
→ Combination of O3, H2O2, and UV light
→ Combination of H2O2 (or O3) and metal ions (e.g. iron salts)
→ Combination of UV light and semiconductors (e.g. TiO2)
→ Electron beam
Commercialized industrial wastewater treatment technologies: Fenton, UV/O3
Fenton’s reaction
• H2O2 + Fe2+  OH + Fe(OH)2+
• Fe(OH)2+ + OH-  Fe(OH)2+
• Fe(OH)2+ +OH-  Fe(OH)3
• In 1894, Fenton found that Fe2+ improves the oxidation capability of H2O2 on tartaric acid
• Substantial amount of ferric hydroxide sludge
• Require solid/liquid separation and disposal

3. TiO2/UV Processes:

 good UV absorption
 low quantum yield (  < 0.03)
Advantages
 No consumable additive
 Use of Solar UV
 Simplicity (easy maintenance). Robustness. Flexibility
 Much lower sensitivity to pH than UV-AOPs based on H2O2 , O3
 Reduction of some pollutants: Mn+, CCl4
Disadvantages
 Separation of the catalyst from the solution
 UV irradiation is poorly utilized by TiO2 despite high absorption
 Poisoning of catalyst by organic matter.
 Low quantum yield
4. Photo Fenton Processes:
Fe+3/UV/H2O2
Fe(III) in the presence of UV :
Fe3+(aq) + H2O + hv  OH· + Fe2+ +H+
 quantum yield for the formation of Fe(II) : 0.14 at 313 nm , 0.017 at 360 nm
Advantages:
 Very cheap
 Simplicity (easy maintenance). Robustness. Flexibility
 Increase mineralization (TOC reduction)
 Use of visible radiation
Disadvantages
 Operation pH 2-4 (optimal =3)
 Generation of sludge through the removal of iron ions.
 Cost of UV-visible lamps
 Waters with suitable UV light transmission
 Fouling of the surface of UV tubes

Sludge:
● The sludge resulting from wastewater treatment operations and processes is usually in the form of a
liquid or semisolid liquid that typically contains from 0.25 to 12 percent solids by weight, depending
on the operations and processes used.
● Sludge is by farther largest in volume and its processing and disposal is perhaps the most complex
problem facing the engineer in the field of wastewater treatment.
● The problems of dealing with sludge are complex because it is composed largely of the substances
responsible for the offensive character of untreated wastewater. The portion of sludge produced from
biological treatment requiring disposal is composed of the organic matter contained in the wastewater
but in another form which can also decompose and become offensive; and only a small part of the
sludge is solid matter.

Preliminary Operation:
Preliminary Operations are used to provide a relatively constant, homogenous feed to sludge-processing
facilities.
1. Sludge Grinding
Sludge grinding is a process in which large and string material contained in sludge is cut or sheared into
small particles to prevent the clogging of or wrapping around rotating equipment.
2. Sludge Degritting
In some plants where separate grit removal facilities are not used ahead of the primary sedimentation
tanks or where the grit removal facilities are not adequate to handle peak flows and peak grit loads, it
may be necessary to remove the grit before further processing of the sludge.
3. Sludge Blending
Sludge from primary, secondary, and advanced processes are blended to produce a uniform mixture to
enhance plant operability and performance.
Blending tanks are usually equipped with mechanical mixers and baffles to ensure good mixing.
4. Sludge Storage
Sludge storage is particularly important in providing a uniform feed rate ahead of the following
processes: lime stabilization, heat treatment, mechanical dewatering, drying, and thermal reduction.
If sludge is stored longer than two or three days, it will deteriorate and will be more difficult to dewater.

Sludge Thickening:
Thickening is a procedure used to increase the solids content of sludge by removing a portion of the
liquid fraction.
1 Gravity Thickening
● Gravity thickening is accomplished in a tank similar in design to conventional sedimentation tank.
Normally, a circular tank is used.
● The supernatant flow that results is returned to the primary settling tank or to the head works of the
treatment plant.
● The thickened sludge that collection the bottom of the tank is pumped to the digesters or dewatering
equipment as required.

Sludge Stabilization
● Sludge is stabilized to
(1) reduce pathogens (2) eliminate offensive odours
(3) inhibit, reduce, or eliminate the potential for putrefaction.
● The technologies for sludge stabilization are
(1) Lime stabilization
(2) Heat treatment
(3) Anaerobic digestion
(4) Aerobic digestion
1. lime stabilization
● In the lime stabilization process, lime is added to untreated sludge insufficient quantity to raise the
pH to 12 or higher.
● Two methods for lime stabilization used are addition of lime to sludge prior to dewatering, termed
“lime pre-treatment” and the addition of lime to sludge after dewatering, or “lime post- treatment”.
● Either hydrated lime, Ca (OH)2, or quicklime, CaO, may be used for lime stabilization.

Sludge Disposal:
1. Beneficial Uses of Sludge
● The fertilizer value of biological sludge, which should be evaluated where the sludge is to be used as
a soil conditioner, is based primary on the content of nitrogen, phosphorus, and potassium.
2. Sludge Disposal
2.1 Landfilling
● There are two types of landfills for industrial sludge: those which accept non-hazardous wastes and
those that accept hazardous wastes.
● Landfills are designed to prevent the contamination of ground water and to prevent the migration of
the wastes from the landfill.
Process:
● For this reason, landfills usually have thick, 3 to 10 feet covers of clean impermeable clay or dirt
on top.
● Landfill bottom and sides are also made of impermeable clays or dirt. The sump collects leachate
from the landfill and is pumped to a wastewater treatment plant.
● Hazardous landfills must meet very stringent requirements. The bottoms and sides must be
double contained, which is usually accomplished by installing two liquid barriers, usually plastic.
● The top of a hazardous waste landfill must be impermeable, which is usually accomplished by
installing a plastic water barrier in the dirt cover.
● Liquid is collected from the space between the barriers in a leachate collection system and is
properly disposed.