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What is an effluent?
Effluence mean flow out; the process of flowing out. And here effluent mean water
mixed with waste matter flowing out of the industry. This water may damage the
aquatic life as well as the earth crust so its treatment I necessary. So here we will
study the effluents from some industries and their treatment methods. In the table
the dangerous components which may be present in the effluent are given with
their limitations.

PARAMETERS TDS CHLORIDE SULPHATES COD BOD DO pH Cr

mg/l mg/l mg/l mg/l mg/l mg/ml mg/l

PERMISSIBL 210 1000 1000 200 30 4-6 6 - ≤

E LIMITS 0 9 0.10

Chlor alkali industry:

Release of waste waters from industries severely affects aquatic flora and fauna.
Effluents from industries involved in the production of pesticides, or from industries
utilizing toxic substances in their production processes are of particular concern.

One such industry is the chlor-alkali industry, utilizes mercury as a cathode in an

electrolytic process. Though no mercury is being utilized in the production process,
losses are inevitable during washings. Release of mercury into the aquatic
environment has received much international attention following the tragedies in
Japan in the 1950s. Since then, attempts have been made to evaluate the toxicity of
effluents in a number of ways.

How to check toxicity of effluent:

One of the most important ways is to determine the minimum concentration of
industrial effluents that kill fish in a particular period. Only with the help of such
bioassay experiments can the toxicity of any pollutant in an effluent be established,
though its toxic effect on aquatic systems also depends on the latter's quantity,
volume and flow of the water, as well as the nature of the bottom sediment. Still,
more valuable is the evaluation of the concentration of the substance which kills
50% of the organisms.

The present study reports the toxicity assessment of the effluent from a chlor-alkali
factory, The reported production capacity of the plant is 50 tons of NaOH per day.
The effluent discharged, 50,000 / per day, contains mercury ranging up to 1.5 mg/l,
much more than the permissible limit of 0.01 mg/l set by the Central Board for the
Prevention and Control of Water, India. The effluent enters the River.

Characteristics which impart a toxic nature to effluent are COD, BOD, mercury,
alkalinity and pH, etc. Values of all parameters were found at high level.

1) Petroleum refinery:
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In most petroleum refineries, the effluent wastewater treatment includes,

(1) Primary Treatment consisting of an Oil-Water separator. No chemical reaction is
involved.
(2) Secondary Treatment consisting of additional oil-water separation using
Dissolved Air Flotation or Dissolved Nitrogen Flotation. No chemical reaction is
involved so no kinetics are involved.
(3) Tertiary Treatment, if any is included, may be one or more of various processes.
However, the most prevalent tertiary treatment is probably biological treatment
such as an activated sludge unit or trickling filter unit. Kinetics is indeed involved in

Pollution Approximate Quantities

Cooling
3.5-5 m3 of wastewater generated per ton of crude
systems
BOD 150-250 mg/l
COD 300-600 mg/l
phenol 20-200 mg/l
Polluted oil 100-300 mg/l (desalter water)
wastewater
oil 5000 mg/l in tank bottom
benzene 1-100 mg/l
heavy metals 0.1-100 mg/l
Solid waste and 3 to 5 kg per ton of crude (80 % should be considered as hazardous waste
sludge because of the heavy metals and toxic organic presence)
VOC emissions 0.5 to 6 kg/ton of crude
BTX (Benzene, Toluene and Xylene) 0.75 to 6 g/ton of crude
Others Sulfur oxides 0.2-0.6 kg/ton of crude
emissions Nitrogen oxides 0.006-0.5 kg/ton of crude

the design of such biological treatment units. In the table impurities contents in the
effluents is given for a petroleum industry.

The petrochemical companies should tackle with several issues:

Salts in the feedstock (corrosion and fouling problems) and

aromatics (source of VOC):
Petroleum refineries do not like salts in their feedstock since these corrode and foul
process equipment. The first refining step is desalination where a hot water wash
extracts the salts. Otherwise it's common to use an antirust or corrosion inhibitors
in the fuel. If feedstock contains aromatics with good solubilities such as Benzene or
Toluene then some will be in the desalted effluent and this is a major source of
refinery wastewater containing Volatile Organic compounds (VOC).

• Aromatics, oil, grease and

organic removal :
A direct treatment of the wastewater with activated carbon reduces aromatics
content to below acceptable limits. In addition, the carbon also captures oil, grease
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and other organics.

Activated carbon is also used to remove heavy hydrocarbons from hydrogen and
light organic gas streams in the refinery.

• Phenol and ammonia cal nitrogen removal with a biological

treatment:
In order to remove phenol and nitrogen the best solution is to use a biological
treatment. Furthermore in using a catalyst combine with the hydrogen per xide it's
possible to remove COD, BOD5 and toxicity of the waste water. Besides, phenols are
transformed into less biodegradable compounds which could be removed by
subsequent coagulation and precipitation.

• The organic and inorganic contaminants from refinery

wastewater :
A process for removing soluble and insoluble organic and inorganic contaminants
from refinery wastewater streams employing ultra filtration and reverse-osmosis is
provided. Before the ultra filtration step, first the wastewater should pass through a
softening system to remove divalent and trivalent metal cations prior to being
passed to the reverse osmosis step to prevent fouling.

• Oily water separation:

One of the main issues of the petrochemical industry is also to remove the oil from
the water after processes or in case of leaks appear in the piping network. In order
to meet the challenge you can use our membrane separation technology. In the
event of alkaline cleaning of tankers, emulsified pollution levels are extremely high.
The correction of the pH is important and it may be necessary to use a mineral
coagulant for instance.

2) Fertilizer industry:
Two acidic streams were considered interesting to focus the initial efforts on: one
rich in nitrate and ammonium ions and another rich in florosilicic and fluoride ions.

This effluent stream comes from the ammonium nitrate fertilizer production unit
through scrubbing of vapors in a packed column with nitric acid. It contains nitrate
and ammonium ions in a concentration range of 200– 500ppm (as nitrogen); it has a
low pH (1–2) and a temperature of 70°C. they are sent to RO membrane.

The target of the RO membrane application is to separate the stream into a small-
volume concentrate that contains the ammonium and nitrate ions and is recycled
into the fertilizer production unit, and into a low-TDS permeate that would reduce
the load of the ion exchange unit for production of boiler feed water, currently
treating city water. In this way water and materials recycling would be achieved. At
the same time improvement of the operation of the ion exchange facility would be
obtained due to reduction in the TDS load and in water and chemicals for
regeneration.
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Florosilicic acid stream:

This stream comes from the phosphoric acid production unit. It contains fluorine and
silicon, mainly in the form of fluorosilicic ions (SiF6 concentrations of 2000–
5000ppm; it has a low pH (1–2) and ambient temperature. Suspended solids of
similar composition are also present.

Initial experimental efforts were focused on raising the pH to neutral levels.

However, this results in the dissociation of florosilicic ions and the formation of
colloidal silica particles, which need to be removed by sedimentation after
coagulant addition (i.e. poly-aluminum chloride). Such a route requires an extensive
pretreatment scheme and the RO concentrate is not considered attractive in terms
of reuse.

For this reason efforts were directed towards treatment of the stream “as is” with
membranes resistant to acidic conditions. Thus, the target of the RO application
under investigation is to concentrate the stream and recycle it in phosphoric acid
production, and at the same time produce a permeate suitable for feeding the ion-
exchange unit.

Flue gas purification:

The amount of air pollutants carried in flue gases and their emission to atmosphere
can be reduced by installation of dedicated purification units in the flue gas path.

1. Emission of particulate matter:

Is reduced or almost eliminated by installation by dust precipitators of numerous
designs and operating principles.

• Centrifugal separators (cyclones):

Cyclones are devices in which particles are caused by means of centrifugal forces to
be propelled to locations outside the gas strem from where they may be removed
and discharged. Reverse flow cyclones are the most common ones with tangential
inlet and axial gas and particle outlet.

• Electrostatic precipitators:
These are the devices in which an electric field is maintained to cause particles to
acquire an electrical charge. The charged particles are forced to travel to a collector
electrode where they are removed and discharged from the process. They are
preferably used for high volume gas streams in power stations, cement plants and
metallurgical plants, etc

• Fabric filters:
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These filters remove particulate matter from gas stream by retention of the
particles in or on a porous structure (bags, beds) where the gas flows through. The
porous structure most commonly a woven or felted fabric, but can also include
materials such as coke, sand, ceramics etc.

• Scrubbers:
They are primarily employ to remove gases or vapor phase contaminant from the
flue gas, but are sometimes used to remove particulate matter.

The particles are brought into contact with a liquid (introduced by sprayers) that
collects the particles in the liquid.

2. Emission of gaseous pollutants:

Can be reduced to certain extent by using low emission fuels, a more effective
reduction is achieved by combustion optimization( fluidized bed combustion or
staggered air supply) and even more by flue gas purification processes such as
adsorption, thermal treatment ,etc

 Flue gas denitrification:

To reduce NOx contents we should have staged combustion by staged air supply
and fluidized bed is used.

By staged air supply in the first stage we will provide the less amount of air and
temperature is also low so less NOx will be produced. In the second stage we will
provide the remaining air necessary for combustion and temperature will be high
now so less NOx will be produced.

 Low NOx burners:

These are also used and they operate on the same principle of staged air.

 Flue gas desulfurization:

The wet scrubbing principle using limestone injection is the most common flue gas
desulfurization process. In the scrubbing tower flue gas is sprayed with a
suspension of ground limestone in water that chemically react with the gaseous
SO2 of the flue gas forming gypsum.

The gypsum is discharged, at least partly, further utilized as building material.

Waste:
The definition of waste can be very subjective, what represents waste to one person
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may represent a valuable resource top another. so waste must have strict legal
definition to comply with the law, because such strict definition of waste have
financial and legal implications for business, local authorities and govt.

Any substance or object which the holder discards or intends to discard. A holder
means the producer of waste or the person who is in possession of it, and producer
means any person whose activities produce waste or any person who carries out
pre processing, mixing or other operations resulting in the change in nature or
composition of the waste.

HARDOUS WASTE:
Hazardous waste is a term used throughout the world to describe waste which is
dangerous or difficult to keep, treat or dispose off, and may contain substances
which are corrosive, toxic, reactive, carcinogenetic, infective. Irritant may be toxic
to the environment.

COMPOSITION OF HAZARDOUS WASTE:

How can be divided into two categories

1. HEALTH HAZARD

CARCINOGEN………………. ALDRINE,FORMALDEHYDE ETC

TOXIC…………………… XYLENE PHENOL etc.

HIGHLY TOXIC……….. HCN ACETONITRILE ETC.

CORROSIVE…………… HF ,H2SO4 SODIUM HYROXIDE etc.

BLOOD DAMAGE ………… NITROTOLUENE BENZENE.

LUNG DAMAGE ………………ASBESTOS SILICA TARS.

EYE DAMAGE …………….SODIUM HYDROXIDE H2SO4.liquid oxygen

2. PHYSICAL HAZARD

Combustible liquids …………………….. Fuel oil crude oil other heavy oil.

Flammable materials …………………….. Gasoline acetone etc.

Explosives……………………………………………. dynamite, nitroglycerine,

ammunition.

TREATMENT & DISPOSAL FOR HAZARDOUS WASTE:

• Recovery
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• Landfill

• Incineration

• Biological treatment

• Chemical treatment

RECOVERY METHOD:
It involves the separation of recoverable materials from hazardous waste by using
separation processes or mechanical separation. Its disadvantage is the recovered
material decreases.

LANDFILLS:
In European countries it is the last option for the disposal of hazardous waste. The
landfill designs in Europe are highly engineered and landfills are natural and
synthetic polymer barriers to contain the waste an prevent the leach ate moving
beyond site boundary each type of waste has its own design.

INCINERATION:
It is 10 to 50 times costly than landfill disposal because flue gas emissions from
incinerator requires extensive clean up system by using electrostatic precipitators’,
scrubbers and bag filters.

Incineration of waste is regarded as thermal treatment process. liquid organic waste

is usually incinerated.

In cement industry, in rotary kilns certain types of waste blended with fuels utilizing
high combustion temperatures greater than 1400celcius.and waste is destroyed by
giving it large residence time. when chlorinated and fluorinated wastes are
combusted the alkaline clinkers from the process, absorbs and neutralizes the acidic
stack gases.

Biological treatment:
1) AEROBIC

2) ANAEROBIC

AEROBIC:
Mostly aerobic activated sludge system is used for the treatment of industrial waste
waster containing organic wastes. Aerobic treatment produces water and carbon
dioxide.
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Waste and micro biological interaction takes place in suspension in a reactor with
residence time 20 to 30 days.

Aerobic supported sludge system has less residence time as compared to activated
system so here product is recycled

ANAEROBIC:
This process occurs in the absence of oxygen here waste is converted in two steps.

1. Converting the waste to organic acids, alcohols, CO2.

2. Breakdown of the acids and alcohols to CO2 and CH4

CHEMICAL TREATMENT:
Neutralization of acidic or alkaline wastes .Removal of inorganic material by ion
exchange resins from solution. Vitrification or solidification where contaminated
soils or sludges are combined with silica containing material at high temp to form a
glass.

Waste Treatment Technologies

The thermal treatment options are generating increasing interest as viable
alternative environmental and economic options for waste processing. These
options have a number of advantages over conventional incineration or land filling
of waste.
Depending on the technology the waste can be processed to produce not only
energy, but also gas or oil products for use as petrochemical feedstock or
carbonaceous char for use in applications such as effluent treatment or for
gasification feedstock. Let's discuss these technologies one by one.

• Pyrolysis
• Gasification
• Composting
• Anaerobic Digestion

Difference between pyrolysis, gasification and combustion

The key difference is the amount of oxygen supplied to the thermal reactor. For
pyrolysis there is an absence of oxygen, and for gasification there is a limited
supply of oxygen, such that complete combustion does not take place, instead the
combustible gases; carbon monoxide and hydrogen are produced. The oxygen for
gasification is supplied in the form of steam, air or pure oxygen. Incineration
involves the complete oxidation of the waste in an excess supply of oxygen to
produce carbon dioxide, water and ash, plus some other products such as metals,
trace hydrocarbons, acid gases, etc.
Flue gas + ash Gasification Gas + Oil + Char
Combustion Gas + Oil + Char Paralysis
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Air No air

Limited air

a. Pyrolysis:
Pyrolysis is the thermal degradation of organic waste in the absence of oxygen to
produce a carbonaceous char, oil and combustible gases. How much of each
product is formed depend on the process conditions, particularly temperature and
heating rate.
Relatively low temperatures are used for pyrolysis, in the range of 400-800C. The
application of pyrolysis to waste materials is relatively recent development. In
particular, the production of oils from the pyrolysis of waste has been investigated,
with the aim of using the oils directly in fuel applications or, after upgrading, to
produce refined fuels.
The oil has a higher energy density that is a higher energy content per unit weight,
than the raw waste. The solid char can be used as carbon black or upgraded to
activated carbon. The gases generated have medium to high calorific values and
may contain sufficient energy to supply the energy requirements of a pyrolysis
plant.

Effects of process conditions in pyrolysis:

The process conditions are altered to produce the desired char, gas or oil end
product, with the pyrolysis temperature and heating rate having the most influence
on the product distribution. The heat is supplied by indirect heating, such as
combustion of gases or oil, or directly by hot gas transfer.

Slow heating:
Very slow heating rates coupled with a low final maximum temperature,
maximizes the yield of char, because the production of char from wood in
the form of charcol involves a very slow heating rate to moderate
temperatures.

Moderate heating:
Moderate heating rates in the range of about 20C/min to 100C/min and
maximum temperature of 600C give an approximately equal distribution of
oils, char and gases. This is referred to as conventional pyrolysis or slow
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pyrolysis.

High heating:
very high heating rates of about 100C/S to 1000C/S at temperatures below
650C and with rapid quenching, lead to the formation of a mainly liquid
product (70%), which is referred to as fast or flash pyrolysis.
At high heating rates and high temperatures the oil products quickly
breakdown to yield a mainly gas product (70%).

Significance of Ash content In Char:

The significance of a high ash content in the chars means that the value of
the char as a fuel is reduced. In addition, the use of pyrolysis chars as
substitutes for activated carbon are greatly diminished if they have high ash
content.

Oil from Pyrolysis:

The product oil from pyrolysis of waste has the advantage of being able to be
used in conventional electricity-generating systems, such as diesel engines
and gas turbines. However it has the problems of high oxygen content, high
viscosity, acidity and polymerization. So research has been undertaken to
upgrade the oils. The research has concentrated on the use of catalysts to
produce a premium quality fuel or high value feedstock.

b. Gasification

Gasification differs from pyrolysis in that oxygen in the form of air, stream or pure
oxygen is reacted at high temperature with the available carbon in the waste to
produce a gas product, ash and a tar product. Partial combustion occurs to produce
heat and the reaction proceeds exothermically to produce a low to medium calorific
value fuel gas.
The operating temperatures are relatively high as compared to pyrolysis, at 800-
1100C with air gasification, at 1000-1400C with oxygen.
Calorific value of the product gas is low for air gasification, in the region 4-6MJ/m3,
and medium, about 10-15MJ/m3 for oxygen gasification.

Quality of product gas:

The characteristics of the gasifier system, the waste composition and operational
conditions can give rise to tars, hydrocarbon gases and chars; these are products of
the incomplete gasification of the waste. The characteristics of the gasifier have
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most influence on the quality of the product gas, for example, down-draft gasifiers
have all the products of gasification passing through a high temperature zone and
with high turbulence. This arrangement results in a high conversion of the pyrolysis
intermediates and a gas with a low tar content, whereas, the updraft gasifier
produces gas which is hot and, when passing up through the down-flowing waste,
produces pyrolysis reactions and a higher concentration of tar in the final product
gas.

Product gases of gasification:

Utilization of the gaseous product is often by direct combustion in a boiler or

furnace. The heat energy is used for process heat or to produce steam for electricity
generation. However, the raw gas will contain tar, char and hydrocarbon gases and
therefore the boiler or furnace burner system must be able to tolerate these
contaminants and not be susceptible to fouling or clogging.
Where the utilization of product gas is into gas turbines or internal combustion
engines to generate power or electricity, then the gas has to be cleaned to a higher
specification than in direct combustion systems. Piping of gas to combustion unit
requires that it be cooled and cleaned before utilization to prevent pipe corrosion
and deposition of tars and water. Removal of particulate material is by cyclones and
bag fitters, and tar removal by secondary cracking at higher cracking or catalyst
cracking at lower temperatures.

c. Composting:
Composting is the aerobic, rather than anaerobic, biological degradation of
biodegradable organic waste. Composting is relatively fast biodegradation
process, taking typically of about 4-6 weeks to reach a stabilized product.

Factors influencing composting:

1) Suitable oxygen content to maintain aerobic conditions: Minimum
oxygen content in the compost of 18% is recommended.
2) Temperature: maximum micro-organism activity is observed in the
temperature range, 30-35 C°
3) Moisture content: below a minimum 40% moisture content,
biodegradation is significantly reduced; high moisture content are also
avoided since they occupy intra particle spaces and there by produce
anaerobic conditions.
4) pH range of waste material: optimum composting is achieved in the pH
range 5.5-8. Bacteria prefer nearly neutral pH, whereas fungi develop better
in a slightly acidic environment.

d. Anaerobic digestion:
The anaerobic degradation processes found in landfills which lead to the formation
of methane and carbon dioxide from organic waste are utilized in anaerobic
digestion but in an enclosed, controlled reactor. The better control of the process
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means that all of the gas is collected for utilization unlike landfills where collection
efficiencies are relatively low at 50% or less.
In addition, the process in a waste landfill typically takes many years to
anaerobically degrade the biodegradable waste, but using an anaerobic digestion
system, the process is complete with in a period of weeks. The solid residue arising
from anaerobic digestion can also be cured and reused as a fertilizer. The main aim
of the process is to produce a product gas, rich in methane, which can be used to
provide a fuel or act as a chemical feedstock.