Treatment on Petrochemical Industry

Waste Water

Presented by: RIMELI

ROY CHOUDHURY
Roll Number:
14/CHE/416

Acknowledgement
I would like to express my special thanks
of gratitude to my teacher Dr. Parimal Pal
for giving me this golden opportunity to
give a presentation on such a wonderful
topic. I learnt a lot of things from this.
Secondly I want to thank my parents and
friends and my seniors for helping me to
complete this project.

AT A GLANCE:

Introduction

Technologies to treat petrochemical industry wastewater

Physico-chemical treatment

Biological treatment petrochemical

Oil Water SeparatorTreatment of oily effluent

Coagulation/Flocculation
Adsorption
Fixed bio-film Reactor
Electrosorption
Membrane Technology

industry wastewater

Aerobic Treatment
Membrane Bioreactor
Sequenching Batch Reactor
Anaerobic Treatment

Chemical Oxidation

Classical Chemical Treatments and

Advanced Oxidation Processes (AOPs)

Conclusion: A Membrane Integrated Hybrid System

References

INTRODUCTION:

Large quantities of wastewater are generated from petrochemical industries .

The discharge of petrochemical wastewater (PCW) could cause serious environmental

pollution and human health concerns as it contains organic and inorganic matter in
varying concentrations.

The quantity and characteristics of wastewater generated from a petrochemical

complex is strongly dependent on individual process plants operating at the complex.

Technologies to treat petrochemical

industry wastewater
In terms of wastewater treatment there are four
classifications of treatment.

Preliminary treatment: It involves the removal of large particles

as well as solids found in the wastewater.

Primary treatment : The second classification is primary
treatment, which involves the removal of organic and inorganic
solids by means of a physical process, and the effluent produced
is termed primary effluent.
Secondary treatment: This is where suspended and residual
organics and compounds are broken down. Secondary treatment
involves biological (bacterial) degradation of undesired products.
Chemical process : The fourth is tertiary treatment, normally a
chemical process and very often including a residual disinfection.

Physico-chemical treatment
Oil Water SeparatorTreatment of oily effluent
Oil and grease in wastewater can exist in several forms: free, dispersed or emulsified. The

differences are based primarily on size. In an oilwater mixture, free oil is characterized
with droplet sizes greater than 150 mm in size, dispersed oil has a size range of 20150
mm and emulsified oil has droplets typically less than 20 mm
Conventional approaches to treat oily wastewaters have included gravity separation and
skimming, dissolved air flotation, de-emulsification, coagulation and flocculation.
Gravity separation followed by skimming is effective in removing free oil from wastewater.
Oil water separators such as the API separator and its variations have found
widespread acceptance as an effective, low cost, primary treatment step. The API oil
water separator is designed to separate the oil and suspended solids from their
wastewater effluents. The API separator, however, is not effective in removing smaller oil
droplets and emulsions.
Emulsified oil in wastewater is usually pre-treated chemically to destabilize the emulsion
followed by gravity separation. The wastewater is heated to reduce viscosity, accentuate
density differences and weaken the interfacial films stabilizing the oil phase. This is
followed by acidification and addition of cationic polymer/ alum to neutralize negative
charge on oil droplets, followed by raising the pH to the alkaline region to induce flock
formation of the inorganic salt. The resulting flock with the adsorbed oil is then separated,
followed by sludge thickening and sludge dewatering.

Coagulation/flocculation
Coagulation/flocculation is one of the most important

processes in the primary purification of water and in

petrochemical wastewater treatment .
Operation Procedure: Coagulants are added to the
tank. The velocity of the water is lowered below the
suspension velocity and the suspended particles
settle down due to gravity. Settled solids are removed
as sludge, and floating solids are removed as scum.
Wastewater leaves the sedimentation tank over an
effluent weir to the next step of treatment.
Governing parameters: Type and dosage of
coagulant/flocculant, pH, mixing speed and time,
temperature and retention time are the governing
parameters to evaluate the efficiency of the process.
Examples of coagulants: Both inorganic and
organic such as aluminum sulfate (alum), ferrous
sulfate, ferric chloride and ferric chloro-sulfate are
widely used as coagulants.
Advantages: This method is widely used as the
primary purification processes mainly due to the ease
of operation, high efficiency, cost effective. Also, it
uses less energy than alternative treatment .
Disadvantages: This treatment process can remove
almost 90% of the suspended solids from the
wastewater but fails to remove organic, inorganic
particles, heavy metals present in the wastewater.

Adsorption techniques to treat wastewater

Adsorption is a natural process by which molecules of a dissolved

compound adsorbs to the surface of an adsorbent solid.

This adsorption method appears to be very promising for the remediation

and recovery of petrochemical waste water.

Granular activated carbon zeolites, silica-aluminas and silicas are the most

popular adsorbent mediums due to their high surface area to volume ratio.
Basic characteristics of

good adsorbents: i) high selectivity due to a

strictly defined chemical composition and porous texture; ii) tunable
hydrophilicity; iii) proven stability under harsh conditions; and iv) in most
cases, excellent regenerability.

Disadvantages: i) most of the adsorbent are temperature sensitive; ii) with

time their adsorption ability may deteriorate; in that case adsorbents need
to be changed after a certain time.

Fixed bio film reactor

The fixed bio film reactor is nothing but a trickling filter that

consists of a bed of highly permeable media on whose surface a

mixed population of microorganisms is developed as a slime layer.
Operation Procedure:

Wastewater passes through the filter

which causes the development of a gelatinous coating of bacteria,
protozoa and other organisms on the media. The continual
increase in the thickness of the slime layer with time which in turns
produce anaerobic end products next to the media surface, and the
maintenance of a hydraulic load to the filter, eventually causes
sloughing of the slime layer to start to form. To prevent clogging of
the distribution nozzles, trickling filters should be preceded by
primary sedimentation tanks equipped with scum collecting
devices. Trickling filters should be followed by secondary
sedimentation tanks to remove the sloughed solids and to produce
a relatively clear effluent.

Advantages: Simple design, trouble free, ease of maintenance

and control nature (as compare to activated sludge process) .

Electrosorption

Electrosorption is nothing but the absorption on surface of

an electrode.
After the polarization of the electrodes, the polar molecules
or ions can be removed from the electrolyte solution by the
imposed electric field and adsorbed onto the surface of the
electrode.
Pros: Electrosorption has attracted a wide interest in the
adsorption processes for treatment of wastewater due to
its environmental friendly and less power consuming
nature.
Cons: It has been limited by the performance of electrode
material.
Activated carbon fibre cloth with high specific surface area
and high conductivity is considered to be the most
effective material which can be used as electrode
materials.

Membrane technology
Application

of membrane based separation processes such as

microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse
osmosis (RO) for treating oily wastewater are increasing day by day.
There are three broad categories of oily wastes free-floating oil,
unstable oil/water emulsions, and highly stable oil/water emulsions
Membranes are most useful with stable emulsions, particularly water
soluble oily wastes. Mechanical separation devices can remove the free
oil by using gravitational force as the driving force whereas unstable
oil/water emulsions can be mechanically or chemically broken and then
gravity separated

Advantages:
Disadvantages:
1.

Widely applicable across a

wide range of industries;

2.

Do not
change;

involve

phase

3.

Higher degree of purity

(99%) can be achieved ;

4.

No separation agent is
required,
making
subsequent oil recovery
easier;

5.

Membranes can be used

in-process
to
allow
recycling
of
selected
waste streams within a
plant;

6.

Energy costs are lower

compared
to
thermal
treatments;

I.

Scale-up is almost linear

above a certain size.

II.

Capital costs for very

large effluent volumes
can be high;

III.

Fouling is the most

important problem in
case of membrane
separation processes.
Due to fouling the flux
decreases with time;

IV.

Clogging is another
important phenomena
which not only decrease
the permeate flux but is
also a reason behind
membrane degradation
during use. Thus
membranes are required
to be replaced frequently,
which can increase
operating costs
significantly.

Biological treatment
petrochemical
industry
wastewater
In the wastewater treatment sector, biological processes deal primary with organic
impurities. Soluble organic sources of biochemical oxygen demand (BOD) can be
removed by any viable microbial process, aerobic, anaerobic or anoxic process.

Aerobic treatment:
Aerobic degradation is a simple, inexpensive and environment friendly way to
degrade wastes.
Governing Parameters:
Parameters which effect the aerobic treatment are
temperature, moisture, pH, nutrients and aeration rate that the bacterial culture
is exposed to, with temperature and aeration being two of the most critical
parameters that determine the degradation rates by the microorganism.
Advantages: i) Aerobic microbial reactions almost 10 times faster than
anaerobic microbial reactions; ii) aerobic reactors can be built relatively small
and open to the atmosphere, yielding the most economical means of BOD
reduction.

Disadvantages: The major disadvantage of aerobic bioprocesses over

anaerobic processes for wastewater treatment, is the large amount of sludge
production due to accumulation of biomass (as biomass yield for aerobic
microorganisms is relatively high, almost 4 times greater than the yield for

Membrane bioreactors
Membrane bioreactors is a combination of the activated

sludge process and a membrane separation process.

Advantages: 1)Decrease in sludge production, 2)improved

effluent quality , 3) efficient treatment of wastewaters with

varying contamination peaks are the different advantages
MBRs offered over traditional activated sludge process.
Disadvantages: Disadvantages of this system include

1)this system needs frequent membrane monitoring and

maintenance, 2)operates at relatively high running costs
and 3) there is a limitation of the pressures, temperatures
and pH the system . 4) Due to membrane fouling proper
designing of these kind of reactor is very difficult. And
because of these reasons MBRs are not being as widely
used in large scale wastewater treatments in comparison to
traditional activated sludge plants

Schematic of conventionalactivated sludgeprocess (top)

and external (side stream) membrane bioreactor (bottom)

SEQUENCING BATCH REACTOR

A sequencing batch reactor (SBR) is a reactor in which an activated sludge process is carried out
in a time oriented, sequential manner using a single vessel for all the phases of the process. The
same steps involved in a conventional, continuous activated sludge process (such as aeration,
pollutant oxidation, sludge settling, and recycling) are now conducted in batch one after the other.

Operating Procedure: It has five discrete periods in each operation cycle: fill, react, settle,
draw, and idle. Reactions start during fill with the reactor nearly empty except for a layer of
acclimated sludge on the bottom and the reactor is then filled up with the wastewater and the
aeration and agitation are started and complete during react. After react, the mixed liquor
suspended solids (MLSS) are allowed to separate by sedimentation during settle in a defined time
period; the treated effluent is withdrawn during draw and the time period between the end of the
draw and the beginning of the new fill is known as idle.

ADVANTAGES:
1)Requirements of chemicals for the overall
treatment process is low,
2) Low operating costs,
3) Eco-friendly and
4) Cost-effective alternative of conventional
techniques and,
5) Efficient at lower levels of contamination.
6) Can accommodate large fluctuations in
the incoming wastewater flow and
composition without failing which may not
get from conventional activated-sludge
processes
7) Even the wastewater residence time in
SBRs can be extended until the microbial
population has recovered and completed the
degradation process and settling time also
can be varied to allow complete settling
before discharging.

DISADVANTAGES:
i) Higher level of sophistication is
required (compared to conventional
systems), especially for larger
systems, of timing units and controls;
ii) Higher level of maintenance
(compared to conventional systems)
associated with more sophisticated
controls, automated switches, and
automated valves;
iii) Potential of discharging floating or
settled sludge during the DRAW or
decant phase with some SBR
configurations;
iv) Potential plugging of aeration
devices during selected operating
cycles, depending on the aeration
system used by the manufacturer;
v) Potential requirement for equalization
after the SBR, depending on the
downstream processes.

ANAEROBIC TREATMENT

Anaerobic reactor differs from the aerobic reactors primarily

because the former must be closed in order to exclude
oxygen from the system while oxygen plays a major role in
case or aerobic reactor.To remove the gazes (mainly
methane and carbon dioxide) produced during anaerobiosis
an anaerobic reactor must provide with an appropriate vent
or a collection system.
Advantages: Anaerobic microbial processes have several
important advantages over aerobic microbial processes like
(1) lower production rate of sludge, (2) operable at higher
influent BOD and toxics levels, (3) no cost associated with
delivering oxygen to the reactor, and (4) production of a
useful by-product, methane (biogas).
Drawbacks of this process: Although anaerobic digestion
provides numerous advantages, it is not extensively applied
in the petrochemical industries due to slow reaction, longer
hydraulic retention time and lack of process stability, higher
capital and operating expenses than aerobic processes
because the anaerobic systems must be closed and heated.

Chemical oxidation

Chemical Oxidation is a process by which electrons are transferred from

one substance to another. which leads to a potential expressed in volts
referred to a normalized hydrogen electrode. The chemical oxidation
processes can be classified in two classes: 1.
2.

Classical Chemical Treatments and

Advanced Oxidation Processes (AOPs)

Classical

chemical treatment: Classical chemical treatments

involves addition of an oxidant agent to the water containing the

contaminant to oxidize it. Some widely used classical oxidants are chlorine,
potassium permanganate, oxygen, hydrogen peroxide, ozonztion etc. This
oxidizer has different advantages and disadvantages. For example,
a)

b)

Chlorine is considered to be a good chemical oxidizer for water evaporation

because it destroys microorganisms. Though it is a strong and cheap oxidant,
very simple to feed into the system. It also has some disadvantages like i) its
little selectivity that high amounts of chlorine are required and ii) it usually
produces carcinogenic organochloride byproducts.
Ozonation is a strong oxidant , does not introduce strange ions in the medium
and has low solubility in water at standard temperature and pressure . Ozone
plays a major role many applications, like the elimination of colour, disinfection,
elimination of smell and taste, elimination of magnesium and organic compounds
etc. As the pH increases, the rate of decomposition of ozone in water also
increases. The major drawbacks of this oxidizer is that it has to be produced on
site and needs installation in an ozone production system in the place of use due

Advanced Oxidation Processes (AOPs):

Among various AOPs like UV/O3 process, UV/H2O2, O3/H2O2, Fe3+/UV-vis

process, UV/TiO2 (Heterogeneous photocatalysis), the Fenton reagent (H 2O2/
Fe2+) is the most effective methods of organic pollutant oxidation.

Fenton process is widely used as a suitable treatment method for highly

concentrated wastewaters due to its effectiveness in producing hydroxyl
radicals.

Application of traditional Fenton process is limited by its acidic pH

requirements, the formation of iron sludge and high cost of hydrogen
peroxide.

But nowadays (EAOPs) based on Fentons reaction chemistry have received

much attention for wastewaters remediation. EAOP is the electro Fenton (EFenton) process, the most popular electro-chemical advanced oxidation
process which can proceed by the following chain reactions:

1)
2)

H2O2 + Fe2+ Fe3+ + OH + OHH2O H+ + OH + e-

(1)
(2)

Conclusion: Membrane integrated hybrid

reactor:

As the petrochemical industries effluents consist of different types of

wastes it cannot be treated by using only one conventional
technique. Several physicochemical options and biological
wastewater treatment processes are showed here which are
technologically and economically feasible and have been widely
utilised in the successful treatment of industrial wastewaters.
API oil separator is an excellent technique for oil removal from
industrial wastewaters whereas both aerobic and anaerobic
treatment systems are feasible to treat wastewater from all types of
industrial effluents. So a combination using an anaerobic process
followed by an aerobic treatment system is a better option but those
hybrid systems produce a high removal of toxic pollutants.
A membrane based integrated system followed by a
coagulation/flocculation process can be applied where the
membrane modules are in cross flow mode to increase the effectivity
of the process; an ultrafiltration (UF) membrane is installed prior to
reverse osmosis (RO) as a pretreatment where UF will remove
emulsions, colloids, macromolecules or proteins (size under 100 nm)
and (RO) will separate dissolved salts and small organics (size under
1 nm).

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