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Treatment of

Petrochemical
Industry Wastewater :
A review
Treatment of Petrochemical Industry Wastewater
including Membrane Technology

Rimeli Roy Choudhury


(14/ChE/2015)
/5/2015

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Treatment of Petrochemical Industry Wastewater : A review

Abstract: The wastewater from a petrochemical complex consists of numerous types of


pollutants including hydrocarbons, in free and emulsified form, phenols including cresols
and xylons, mercaptans, sulphides, ammonia and cyanide. In this review paper, various
industrial wastewater treatment technologies which are currently available are discussed. An
extensive list of various methods of removal of mercury, chromium, cadmium, sulphur,
nitrogen and other heavy metals and COD from petrochemical industry wastewater has been
discussed.

Introduction:
Petrochemical Industry is one of the fastest growing core sectors of the economy. As a
result, many petrochemical plants of different sizes and technologies co-exist at the present
time. The petrochemical industry is highly technological and capital-intensive. Technologies
for petrochemical industries have been developing very fast. Tremendous resources and
efforts are being continuously spent on increasing size and yield of plants through
continuous upgrade of catalyst, reducing energy consumption and cost reduction through
novel process rate, new chemistries or scale up approaches. The petrochemical industry is a
complex and is an integrated industry that includes a large variety of processes and products.
Because of a large number of processes, use of wide variety of raw materials, catalysts,
additives, chemicals, presence of explosives and hazardous materials, the problem of
environmental pollution from petrochemical industries is also quite complex.
A wide variety of pollutants is discharged into water stream and emitted into the
environment. The quantity and characteristics of wastewater generated from a petrochemical
complex is strongly dependent on individual process plants operating at the complex.
Wastewater generated from ethylene cracker are inorganic sulphides, mercaptans, soluble

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Treatment of Petrochemical Industry Wastewater : A review

hydrocarbons, polymerised product, phenolic compounds, sulphide, cyanide, heavy oils,


coke, spent caustic, SOx, NOx, hydrocarbons, particulates, water borne waste containing
BOD, COD, suspended solid, oil and those from aromatic plants are dissolved organics,
volatile organic compounds, heavy metals, hydrocarbons, particulates, H 2S, SOx, NOx, CO,
water borne waste containing BOD, COD, suspended solid, oil & grease, toluene, benzene,
xylenes, HCl, chlorine, cadmium. These pollutants can lead to several direct effects on
social and environmental health and almost appears in three dimensions of water, soil and
vibrations. The most considerable is water and soil pollution which had the most effect on
local ecosystems. As there are several pollutants present in the wastewater effluent from the
petrochemical industry so several techniques have been developed to omit or reduce the
contamination of these pollutants. Treatment of petrochemical waste water to minimize its
environmental impact has caught the devotion of researchers over the last few decades
towards the development of an environment-friendly cost effective continuous method.
Amidst the growing stringent discharge rules all over the world, petrochemical industrial
houses has to suffer due to the formation of verities of wastes formed inside the industry.
Moreover, the treatment methods prior to discharge should be cheaper because the recovery
and discharge processes by separation and purification technology plays a major role in
hiking up the cost of a complete process. Hence, our aim is to find a sustainable green and
clean technology under reduced conditions of energy, material and energy and cost
consumption with a promise to achieve higher engineering flexibility to the plant and lowest
environmental impacts. Thus old, inefficient, energy intensive technologies should be
replaced with new, smaller, safer and modular designed equipment.
Large amounts of nitrogen and sulphur presents in wastewater effluent coming from
catalytic hydro-cracking unit of petrochemical industries, in the form of ammonia (NH 3) and
hydrogen sulphide (H2S), respectively. Hydrogen sulphide, one of the main constituents of

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Treatment of Petrochemical Industry Wastewater : A review

petrochemical industry effluents is a toxic and corrosive gas that causes environmental and
economic problems in a variety of sectors. Some researcher has proved that one of the best
way to control and remove sulphide is the use of nitrate [1,2,3]. Presence of ammonia and its
derivatives in water effluent from petrochemical industry are one of those reasons which are
responsible for water pollution. Various researches have been done for biological settlement
of wastewater contaminated by ammonia and its derivatives. There are a number of aerobic
and anaerobic microorganisms are there which are able to express the enzyme urease (urea
amidohydrolase) which catalyses the hydrolysis of urea [4,5]. Copper and chromium are
another two most common metals found in wastewater discharge of petrochemical plants
wastewater discharge from other industrial sites [6] where hexavalent chromium, Cr(VI)
present at concentrations ranging from tenths to hundreds of mg/L [7]. Mirbagheri et al.[8]
used ferrous sulfate and lime Ca(OH)2 for pH adjustment and conversion of Cr(VI) to
Cr(III) and Cr(III) precipitation, respectively. 9647167200
The largest industries which produce wastewater containing mercury and cadmium are vinyl
chloride monomer and PVC producing petrochemical factories. Malakahmad et al. has
performed a lab-scale experiment with a Sequencing Batch Reactor (SBR) to treat a
synthetic petrochemical wastewater containing mercury and cadmium. [9]. Wastewater of
petrochemical industries also contains high amounts of emulsified aliphatic or aromatic
hydrocarbons. Taran has showed Haloarcula sp. IRU1 can degrade petrochemical
wastewater and produce PHB from it in different conditions [10].
Membrane technologies have became the most popular separation process for treatment of
petrochemical industry wastewater. Now-a-days it is also competing with traditional
schemes [11-15]. Membrane separation processes have various advantages like a) 100%
purity of product can be achieved, b) low energy consumption, 3) compared with other
conventional techniques, membranes can offer a simple, easy-to-operate, low-maintenance

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Treatment of Petrochemical Industry Wastewater : A review

process option, c) no external chemicals are required to add for separation, d) can operate at
a moderate temperature and pressure. With all of these advantages there are also certain
disadvantages of this membrane based separation processes; Cake formation or fouling can
be considered as a major problem of membrane based separation processes which is the
main reason for reduction of permeate flux. But this problem can also overcome by using
cross flow arrangement and using different types of membrane modules.
From this perspective of mindset, the sincere contribution towards environment and
reduction of operating cost by process intensification has triggered our effort towards
membrane based processes. Pressure-driven Reverse Osmosis being comparatively an
innovative one, possess the ability to stand as a viable solution replacing conventional
separation and purification techniques like distillation, evaporation ion exchange, absorption.
Being modular in design, membrane based plants are able to ensure the possibility of
operation in a simpler plant with a required number of active units which offers high
flexibility to the plant. By the virtue of high selectivity membranes are able to offer high
degree of separation and purification (over 98%) to the targeted molecules. Membrane based
processes are highly efficient to act as a perfect substitute to the conventional unit operation
techniques like distillation, condensation or absorption; in an eco-friendly way while
involving less man power or electrical energy. Due to no involvement of phase changing
phenomena; energy and cost consumption can be efficiently reduced while implementing
membrane technology at the industrial level for product purification. Membrane based
processes employing highly selective membranes offer a high degree of separation and
purification with high permeate flux. Membrane based reactors are easy to design and easier
to scale up. Proper utilization of raw materials by continuous recycling and recovery of
byproducts could be efficiently performed using such technologies. Consequently they
ensure a compact design while reducing the capital cost. So a properly designed membrane

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Treatment of Petrochemical Industry Wastewater : A review

integrated hybrid treatment system employed for effective removal of wastes from
petrochemical refinery effluents is expected to overcome all the technology barriers as
discussed previously. Thus evidently membrane involved process schemes can meet all the
aims of process intensification and sustainable industrialization. In this case our goal is to
dedicate ourselves to some environment friendly, economically feasible continuous
production scheme for the proper treatment of petrochemical waste water, eliminating the
drawbacks associated with conventional processes. In this paper, a brief discussion about the
traditional treatment has been provided highlighting the major drawbacks associated with
them.

Control Techniques
The control technology is to be based upon the most exemplary combination of in-process
and end-of-process treatment & control technologies. This level of technology is primarily
based upon significant reductions in the COD, as well as the BOD. End-of-pipe treatment in
this case will be biological plus additional activated carbon treatment. The techniques that
can be applied to new plants and to existing facilities will differ. In existing plants, the
choice of control techniques is usually restricted to process integrated (in-plant) control
measures, in-plant treatment of segregated individual streams and end-of-pipe treatment.
New plants provide better opportunities to improve environmental performance through the
use of alternative technologies to prevent wastewater generation. An appropriate control
strategy for waste water from the Petrochemical industry can be summarized as:
(a) Organic wastewater streams not containing heavy metals or toxic or non biodegradable
organic compounds are potentially fit for combined biological wastewater treatment (subject
to an evaluation of biodegradability, inhibitory effects, sludge deterioration effects, volatility
and residual pollutant levels in the effluent).

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Treatment of Petrochemical Industry Wastewater : A review

(b)Wastewater streams containing heavy metals or toxic or non-biodegradable organic


compounds (e.g. indicated by high AOX /EOX or high COD/BOD ratios) are preferably
treated or recovered separately. Individual waste streams containing toxic or inhibitory
organic compounds or having low bio-degradability are treated separately e.g. by (chemical)
oxidation, adsorption, filtration, extraction, (steam) stripping, hydrolysis (to improve
biodegradability) or anaerobic pretreatment.
Technologies to treat chemical industry effluents
There are mainly four stages of petrochemical industry wastewater treatment. First is
preliminary treatment which involves the removal of large particles as well as solids found
in wastewater samples. Second is primary treatment, which involves the removal of organic
and inorganic solids by means of a physical process, and the effluent produced is termed as
primary effluent. The third treatment is called secondary treatment; this is where suspended
and residual organics and compounds are broken down. Secondary treatment involves
biological (bacterial) degradation of undesired products. 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
Petrochemical industries report high levels of oil and grease in their effluents (with an Oil
and grease concentration up to 200,000 mg/l) [16,17]. Oil and grease presents in wastewater
can be either of these forms: free, dispersed or emulsified where 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. Oil and grease concentrations in
wastewater can be measured by different test procedures of the US Environmental
Protection Agency but they failed to determine the presence of specific compounds. Gravity

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Treatment of Petrochemical Industry Wastewater : A review

separation and skimming, dissolved air flotation, de-emulsification, coagulation and


flocculation are the several conventional approaches of treating oily wastewaters. Gravity
separation followed by skimming is effective in removing free oil from wastewater whereas
the API oil water separator is designed to separate the oil and suspended solids from their
wastewater effluents. But this is not effective in removing smaller oil droplets and
emulsions. Primary clarifier is used to remove the oil that adheres to the surface of solid
particles.
Wastewater is usually pre-treated chemically to destabilize the emulsified oil followed by
gravity separation. The wastewater is also heated to reduce viscosity and density differences
and to weaken the interfacial films stabilizing the oil phase which is followed by
acidification and addition of cationic polymer/ alum for the neutralization of negative
charges on oil droplets. While waste water treatment, pH is kept at some high value
(alkaline regime) to induce flock formation of inorganic salts. The resulting flock with the
adsorbed oil is then separated, followed by sludge thickening and sludge dewatering.

Coagulationflocculation
Coagulation/flocculation is one of the most important processes in the primary purification
of water and in petrochemical wastewater treatment [18-20]. 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 [20-22]. It is also called
clarification in which 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. Factors such as the type and dosage of

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Treatment of Petrochemical Industry Wastewater : A review

coagulant/flocculant, pH, mixing speed and time, temperature and retention time are the
governing parameters to evaluate the efficiency of the process [26] . Both inorganic and
organic such as aluminum sulfate (alum), ferrous sulfate, ferric chloride and ferric chlorosulfate are widely used as coagulants in petrochemical industry wastewater treatment for
removing a broad range of impurities from effluent, including organic matter, turbidity,
colour, microorganism, colloidal particles and dissolved organic substances [19,20,23,25].
Altaher et al. [27] demonstrated in his paper that the pH plays a significant role in
coagulation-flocculation process. The experiments conducted showed that increase in pH
form acidic range to alkaline range promotes turbidity removal which also indicates that the
pH played a significant role in imparting surface charge of organic and inorganic colloids.
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 becomes economically unviable for
the removal of heavy metals at lower concentrations and thus it 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. Zeolites have some peculiar
characteristics, which include 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 [28]. Zeolite can remove heavy-

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Treatment of Petrochemical Industry Wastewater : A review

metal-cation by applying cation exchange technique [29], have a wide spectrum of


amorphous molecular sieve materials which make them markedly different from natural
zeolites. Due to their i) wide pore openings, ii) high specific surface areas and iii) large
specific pore volumes, silica-aluminas and silicas have drawn attention for their adsorption
of major amounts of non-dissociated contaminants characterized by bulky molecules (which
are unable to diffuse through zeolite micropores) that have been dissolved or even dispersed
in water as oily droplets. Many research studies have been done where non-conventional
adsorbents, such as agricultural and industrial solids wastes are used for the removal of
heavy metals [30-32]. There are other materials which have also been used to remove heavy
metals from wastewater, such as peat, wool, silk, and water hyacinth. Many researchers have
worked on preparation of activated carbon from cheaper and readily available materials
[31,32].
Maretto et al.[33] used two different microporous materials, a natural zeolite called
clinoptilolite and a polymeric chelating resin named Purolite_ Resin S910, to remove
dissolved heavy metals, and a mesoporous siliceous material to uptake hydrocarbons from
wastewater. The batch experiments indicated a good adsorption rate and a percentage of
heavy metal (Pb2+, Cd2+ and Ni2+) and hydrocarbon removal (benzene and toluene) that was
always greater than 90%. They developed a new adsorption model to better describe the
adsorption mechanism of heavy metals and a two-step mechanism for hydrocarbons. Here
both of the materials seemed to maintain good adsorption capabilities. It was also showed in
this experiment that increase in ionic strength tends to decrease the adsorption performance
of the microporous material and the presence of organic interfering contaminants.
But with all the advantages described above adsorption technique also posses certain
disadvantages like i) most of the adsorbent are temperature sensitive; ii) with time their

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Treatment of Petrochemical Industry Wastewater : A review

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. 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.
With the advantages of its simple design, trouble free, ease of maintenance and control
nature (as compare to activated sludge process) trickling filter also has some disadvantages
such as

excessive organic loading without a corresponding higher recirculation rate

clogging of under drain system, non-uniform media size or breaking up of media.

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

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Treatment of Petrochemical Industry Wastewater : A review

electrode. Electrosorption has attracted a wide interest in the adsorption processes for
treatment of wastewater due to its environmental friendly and less power consuming nature.
But 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 freefloating oil, unstable oil/water emulsions, and highly stable oil/water emulsions of which
membranes are most useful with stable emulsions, particularly water soluble oily wastes
[34]. 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. Cheryan et al. [35] reported a study where a semi-batch
type recycle membrane unit was employed. A constant level was maintained in the process
tank adding wastewater feed at a rate equal to the rate of withdrawal of clean permeate and
retantate stream containing oil and grease was recycled back to the process tank. When the
oils and grease and other suspended matter reached a certain predetermined concentration in
the tank, the feed was stopped and the retentate allowed to concentrate which finally gave a
result of final concentrate volume that was only 3-5% of initial volume of oily wastewater.

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Treatment of Petrochemical Industry Wastewater : A review

Fig. 1. Schematic of typical membrane system for treatment of oily wastes (adapted from Cheryan [24])

Membranes have several advantages, among them: (1) Widely applicable across a wide
range of industries; (2) Do not involve phase change; 3) The membrane is a positive barrier
to rejected components. Separation process can have a higher degree of purity (99%) than
other processes; (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; (7) The plant can be
highly automated and does not require highly skilled operators. Membrane processes have
some limitations: (i) Scale-up is almost linear above a certain size. Thus capital costs for
very large effluent volumes can be high; (ii) Fouling is the most important problem in case
of membrane separation processes. Due to fouling the flux decreases with time; (iii)
Clogging is another important phenomena occurs in membrane separation process 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. Several researches has been done to mitigate this problem; according to
which the use of vibratory or centrifugal devices to enhance shear at the membrane surface
to decrease concentration polarization, modification of membrane surfaces to increase
hydrophilicity, and pre-treatment of feed are the most effective techniques to be followed.

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Treatment of Petrochemical Industry Wastewater : A review

[36,37]. In spite of the above disadvantages, membrane processing of oily wastewaters,


sometimes in conjunction with other methods for treating the residuals is widely used for the
treatment of wastewater all over the world.
Fratila-Apachitei et al. [38] has reused petrochemical effluent as cooling water after treating
it by a scheme comprising of ultrafiltration and reverse osmosis. They have used RO
membrane to decrease the salinity to an allowable level for reuse as cooling water followed
by a dead-end UF membrane which was used to reduce the turbidity of the wastewater. They
performed UF test at constant transmembrane pressure (0.2 bar) using hollow fibre
polyethersulphone membranes coated with poly-vinyl-pirrolidone. To compare the
performance characteristics two membranes with different molecular sizes(50 and 150 kDa)
were taken and performed separately where the 150 kDa membrane showed a very fast flux
decline (i.e. 20% in 2 min) requiring frequent backwashing (BW), whereas 50 kDa
membrane showed a relatively slow flux decline i.e. 20% flux in 20 min. As a gradual
change from complete to intermediate blocking and cake filtration was observed in both
cases, analysis of the blocking mechanisms failed to explain the rapid drop in flux for the
150 kDa membrane as compared with the 50 kDa membrane. But a field emission scanning
electron microscopy (FESEM) analysis of both UF membranes suggested that the highly
interconnected pore system of the 50 kDa membrane is mainly responsible for filtration
performance which in turns result in a 3D-bridge-type surface morphology.
On the other side Teodosiu et al. [39] also worked on to evaluate the possibilities of using
UF as a pre-treatment for RO, in a double membrane filtration scheme where the two UF
membrane provided by the same manufacturer, made of polyetherosulphone /
polyvinylpirollidone) with the same molecular weight cut-off of 150,000 Da but with
different coatings have been used. They showed that the low fouling membrane is easy to

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Treatment of Petrochemical Industry Wastewater : A review

clean by backwashing or enhanced backwashing, having a better flux restoration and a


higher efficiency as production and operation and application of the polymer coating for the
low fouling membrane, although decreases permeability, has a positive effect concerning
membrane A-LF performance. Experimentally they have proved that ultrafiltration offers
almost complete removal of suspended solids and colloids (98% as turbidity) and partial
removal of organic compounds attached to suspended solids (30% as COD) and thus
ultrafiltration can be considered to be a good pre-treatment for a reverse osmosis process,
which has to remove further dissolved inorganic and organic compounds, in order to achieve
the requirements for recycling [40].

Biological treatment of petrochemical industry wastewater


Aerobic treatment
In the wastewater treatment sector, biological processes deal primary with organic
impurities. Aerobic degradation is a simple, inexpensive and environment friendly way to
degrade wastes. 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. Soluble organic sources of biochemical oxygen demand (BOD) can be
removed by any viable microbial process, aerobic, anaerobic or anoxic of which the aerobic
microbial reactions almost 10 times faster than anaerobic microbial reactions. Thats why
aerobic reactors can be built relatively small and open to the atmosphere, yielding the most
economical means of BOD reduction. With the advantages aerobic bioprocess also have
certain disadvantages. The major disadvantage of aerobic bioprocesses over anaerobic
processes for wastewater treatment, is the large amount of sludge production due to

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Treatment of Petrochemical Industry Wastewater : A review

accumulation of biomass (as biomass yield for aerobic microorganisms is relatively high,
almost 4 times greater than the yield for anaerobic organisms).

Membrane bioreactors
Membrane bioreactors is a combination of the activated sludge process and a membrane
separation process. A simplified MBR diagram is shown in Figure 2.

Figure 2: Diagram showing the basic configuration of a membrane bioreactor [27]

A decrease in sludge production, improved effluent quality and efficient treatment of


wastewaters with varying contamination peaks are the different advantages MBRs offered
over traditional activated sludge process. Some disadvantages of this system include this
system needs frequent membrane monitoring and maintenance, operates at relatively high
running costs and there is a limitation of the pressures, temperatures and pH the system
which are considered as the basic disadvantages of the system. 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 [41,42].

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Treatment of Petrochemical Industry Wastewater : A review

Khaing et al.[43] treatment petrochemical industry wastewater from a petrochemical using a


novel submerged membrane distillation bioreactor (MDBR) proved that it is feasible to treat
and reuse the wastewater using submersed MDBR technology. But the pitfalls are same as
that in MBR including flux declination is also plays a major role due to inorganic fouling of
the membranes.

Sequencing batch reactor


Conventional methods to remove heavy metals petrochemical industry wastewater usually
involve physico-chemical treatments such as precipitation, ion exchange, electrondeposition [44]. There are some major problems associated with these methods such as they
are more costly compared to biological treatment methods and can themselves produce other
waste problems; which limited their industrial applications [45,46]. Among the available
treatment methods, sequencing batch reactors (SBRs)

has caught attention due to some

reasons such as reduced chemicals requirement for the overall treatment process, low
operating costs, eco-friendly and cost-effective alternative of conventional techniques and,
efficient at lower levels of contamination [47]. Other than these the main advantage of SBRs
is that they can accommodate large fluctuations in the incoming wastewater flow and
composition without failing which may not get from conventional activated-sludge
processes, in which an increase in the incoming flow rate results in a lower residence time of
the wastewater in the aeration tank and of the sludge in the clarifier, with potential failure of
one of them or both. 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. A SBR is an activated
sludge process periodically operated, fill-and-draw reactor [48] which has five discrete

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Treatment of Petrochemical Industry Wastewater : A review

periods in each operation cycle: fill, react, settle, draw, and idle [44]. 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 [49]. Researchers have been working on it and a
number of papers also have been published which provide good description and evaluation
of the SBR systems in treatment of heavy metals [44,5052].
Malakahmad et al [53] treated synthetic refinery wastewater containing Hg 2+ and Cd2+, in a
SBR after acclimated the system for 60 days. The SBR was first introduced to mercury and
cadmium in low concentrations which then was increased gradually to 9.030.02 mg/L Hg
and 15.520.02 mg/L Cd until day 110. The study revealed that the COD removal efficiency
ranged from 66 to 88% before addition of heavy metals due to appropriate acclimatization
of the biomass during start-up period and adequate retention of MLVSS concentration which
contributed to high COD removal efficiency. MLVSS concentration (population of
microorganisms) which showed an appreciable growth during reactor start-up and reached
to 1870 mg/L, was affected by heavy metals concentration increment in each step and
finally its concentration has fallen to 510 mg/L. Heavy metals added to the SBR decrease
the settleability of the sludge . The study also showed that at maximum concentrations of the
heavy metals, the SBR was able to remove 7690% of Hg2+ and 9698% of Cd2+.
With all the advantages there are certain drawbacks associated with this method such as: i) a
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

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Treatment of Petrochemical Industry Wastewater : A review

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. 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). According to Yerushalmi et al.
[54], addition of a co-substrate increases the biogas potential due to a well-equilibrated
medium and the accumulation of limiting nutrients. Manure is considered to be a superb cosubstrate, due to its ability of providing buffering and many nutrients important for
microbial development (Sambusiti et al.[55], Yang and Liu [56]). Siddique et al. [57]
operated anaerobic co-digestion (ACD) of petrochemical wastewater (PWW) and activated
manure (AM) in a continuous stirred tank reactor where he achieved an 80% methane yield
of 11.1 m3 m-3 d-1 with 98.57 0.5% elimination of chemical oxygen demand at five days'
hydraulic retention time using a ratio of 50% PWW/50% AM. Although anaerobic digestion

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Treatment of Petrochemical Industry Wastewater : A review

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: - 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 [58]classical
oxidants are chlorine, potassium permanganate, oxygen, hydrogen peroxide, ozonztion etc.
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 [58]. 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.
Hydrogen peroxide is a multipurpose oxidant can be applied directly or with a catalyst.
Ferrous sul[hate, Al3+, Cu2+ or other iron salts are generally used as catalyst. Its basic
advantages are: (i) low cost (ii) it has high oxidizing power, (iii) easy to handle), (iv)watersoluble (v) it does not produce toxins or colour in by products vi) it can also been used in
presence of ultraviolet. Ozonation is a strong oxidant that presents the advantage of both
hydrogen peroxide and oxygen. It does not introduce strange ions in the medium and has
low solubility in water at standard temperature and pressure [58] . Ozone plays a major role

21
Treatment of Petrochemical Industry Wastewater : A review

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 to which the cost of this oxidizer is extremely high.
Advanced Oxidation Processes (AOPs): Among various AOPs like UV/O 3 process,
UV/H2O2, O3/H2O2, Fe3+/UV-vis process, UV/TiO2 (Heterogeneous photocatalysis), the
Fenton reagent (H2O2/ 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 [59,60]. Application of
traditional Fenton process is limited by its acidic pH requirements, the formation of iron
sludge and high cost of hydrogen peroxide [59,61]. But nowadays (EAOPs) based on
Fentons reaction chemistry have received much attention for wastewaters remediation [61].
EAOP is the electro Fenton (E-Fenton) process [62], the most popular electro-chemical
advanced oxidation process which can proceed by the following chain reactions [62-63]:
H2O2 + Fe2+ Fe3+ + OH + OH-

(1)

H2O H+ + OH + eFe3+ + e- Fe2+

(2)
(3)

Davarnejad et al. conducted an experiment where he compared aluminum and iron plate
electrodes on COD and colour removal from Petrochemical wastewaters and also evaluated
the effects of reaction time, current density, pH, H 2O2/Fe2+ molar ratio, and H2O2

of

petrochemical wastewater (PW)(ml/l) on the performance of the process. The results


revealed that COD and colour removal efficiencies of iron electrode were (67.3% and

22
Treatment of Petrochemical Industry Wastewater : A review

71.58%, respectively) which were more than those of aluminum electrode (53.94% and
67.35%, respectively). However, some disadvantages are also there in using the Fenton
reagent which are i) the production of a substantial amount of Fe (OH) 3 precipitate and ii)
additional water pollution caused by the homogeneous catalyst that added as an iron salt,
cannot be retained in the process [58]. A number of researchers have investigated the
application of iron oxides such as hematite, ferrihydrite, semicrystalline iron oxide and
crystalline goethite [58] where they have observed a greatly accelerated decomposition of
hydrogen peroxide but variable amounts of contaminant were lost.

Conclusion
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).

23
Treatment of Petrochemical Industry Wastewater : A review

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