Beruflich Dokumente
Kultur Dokumente
Petrochemical
Industry Wastewater :
A review
Treatment of Petrochemical Industry Wastewater
including Membrane Technology
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Treatment of Petrochemical Industry Wastewater : A review
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
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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
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
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.
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Treatment of Petrochemical Industry Wastewater : A review
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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.
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
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Treatment of Petrochemical Industry Wastewater : A review
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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.
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Treatment of Petrochemical Industry Wastewater : A review
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
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
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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)
(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
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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).
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Treatment of Petrochemical Industry Wastewater : A review
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Treatment of Petrochemical Industry Wastewater : A review
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Treatment of Petrochemical Industry Wastewater : A review
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