Journal of Environmental Chemical Engineering 7 (2019) 103326

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Current technologies and future directions for treating petroleum refineries T

and petrochemical plants (PRPP) wastewaters
⁎
Shahryar Jafarinejada,b, , Sunny C. Jianga
a
Civil and Environmental Engineering, University of California, Irvine, CA, USA
b
Department of Chemical Engineering, College of Engineering, Tuskegee University, Tuskegee, AL, USA

A R T I C LE I N FO A B S T R A C T

Keywords: Water scarcity and wastewater management pose significant challenges to petroleum refineries and petro-
Petroleum chemicals plants (PRPP). The escalating demand of petroleum products in pace with the world population
Wastewater treatment plant growth and technological development requires new water management strategies that encourage reducing
Refinery water consumption, reusing treated wastewater and remediating environmental impacts (R3). New innovations
Petrochemical
and design of PRPP wastewater treatment plant (WWTP) are necessary to incorporate the principal of R3 to meet
both the industrial water needs and the environmental regulatory requirements. The goal of this review is to
summarize the state of technologies for wastewater treatment in the PRPP in order to identify areas of future
improvements. We begin with a systematic survey of water quality characteristics of PRPP discharge and the
regulatory requirements for effluent water. We then examine the current WWTP technologies, configuration and
operation in managing PRPP wastewaters, followed by discussion on PRPP WWTPs in Iran. Lastly, based on the
gaps identified in the system analysis, we share our vision for future opportunities in improving the design and
operation of PRPP WWTPs. Specifically, we recommend new hybrid technologies to increase treatment capacity,
improve effluent water quality, and manage shock loadings of toxic materials and organics.

1. Introduction generates large amounts of wastewater [8]. Discharging of these ef-

The need for petroleum and other energy resources are growing
with the population growth and worldwide economic development. The
global energy demands are expected to increase 37% from the current
level by 2035 [1,2] with a large portion of the energy relying on pet-
roleum products. However, scarcity of water resources and concerns of
environmental pollution [3–5] present great challenges to petroleum
industry. The nexus of water and petroleum energy production is now
well recognized. New water management and wastewater treatment
strategies are critically needed to help the petroleum industry and to
protect the environment.
The petroleum industry can roughly be divided into four sectors: 1)
exploration, development and production; 2) hydrocarbon processing
(refineries and petrochemicals plants); 3) storage, transportation, and
distribution; and 4) retail or marketing [6–8]. These four sectors are
also known as upstream, midstream and downstream processes [9,10].
Although environmental impacts are associated with every sector of the
industry, hydrocarbon processing by petroleum refineries and petro-
chemicals plants (PRPPs) uses the largest amount of water and also
fluents without effective treatment technologies to separate water and
oil not only pollutes the environment but also reduces the product re-
covery and misses the opportunity for recycle the water for reuse in
other PRPP processes [8,11,12].
Worldwide, PRPP produces more than 2500 different types of va-
luable products from crude oil [13]. In 2015, approximately 95 million
barrel per day (mbpd) of oil was consumed globally, up from 84.7 mbpd
in 2005 [14]. The amount of water required and wastewater produced
depends on the size of the plant, type of crude oil used, products gen-
erated and the complexity of operation [4,15]. It is estimated that
80–90% of the water supplied to PRPP comes out as wastewater since
water does not enter into the final product [8,16]. According to Coelho
et al. [17], petroleum refinery processes generate around 0.4–1.6 times
the volume of wastewater per volume of crude oil processed [4,17].
Thus, based on 95 mbpd of consumed oil in 2015, PRPP would generate
between 38 and 152 mbpd of wastewater globally. The PRPP process
configuration can affect the quantity and quality of the wastewaters
generated greatly. For example, only 3.5-5 m3 of wastewater is gener-
ated per ton of crude oil processed when cooling water is recycled

⁎
Corresponding author at: Civil and Environmental Engineering, University of California, Irvine, CA, USA; Department of Chemical Engineering, College of
Engineering, Tuskegee University, Tuskegee, AL, USA.
E-mail address: sjafarinejad@tuskegee.edu (S. Jafarinejad).

https://doi.org/10.1016/j.jece.2019.103326
Received 10 March 2019; Received in revised form 13 July 2019; Accepted 27 July 2019
Available online 29 July 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
S. Jafarinejad and S.C. Jiang Journal of Environmental Chemical Engineering 7 (2019) 103326

[8,18,19]. However, petrochemical plants generate 131,400 m3 waste- Table 1

water per 500,000 metric tons ethylene production annually [8,20]. List of commonly measured water quality parameters in PRPP wastewater and
Wastewaters are produced by different processes and operations in World Bank Group (WBG) effluent discharging guidelines.
PRPP. Some wastewaters are generated directly from production pro- Parameters Typical PRPP Wastewater WBG Guidelines [31]
cesses such as vapor condensation, process water and spent caustic in
crackers, and aromatic plants. Others are from cooling tower blow mg/L mg/L
O&G 12.5 – 20223 10
down, pump and compressor cooling. Surface runoff from paved utility
BOD 90 – 685 30
area drains collecting stormwater contaminated by crude oil, chemical COD 300 – 600 125
solvents, and spilled petroleum products is another significant source of TSS 28.9 – 950 30
environmental pollutants from PRPP [8,20–23]. Large PRPPs also Phenol 0.2 – 200 0.2
pH 6.7 - 10.8 6–9
generate considerable quantity of sanitary wastewater [22,21–23].
Turbidity 10.5 - 159.4 (NTU)
These diverse types of wastewater may be combined in some cases but BTEX 1 -100
can be also segregated during treatment processes. Benzene 0.05
It is clear that effective wastewater treatment and reuse technolo- Benzo(a)pyrne 0.05
gies are crucial to manage the wastewater from the PRPP [24]. Such Total cyanide 1
Free cyanide 0.1
technologies are beneficial to petroleum industries by: 1) providing
Heavy metals 0.01 – 100
additional source of water through water recycling, 2) improving the Total Chromium 0.5
crude oil recovery, and 3) reducing and remediating the impact to the Hexavalent Chromium 0.05
environment [4]. The strategy of recycle, reuse and reduce (R3) should Copper 0.5
Iron 3
be incorporated as a fundamental principal for the design and operation
Lead 0.1
of future PRPP wastewater treatment plants (WWTPs). In this study, we Nickel 0.5
carried out a review and analysis on quantity and quality of wastewater Mercury 0.03
effluent from PRPP. We conducted literature research to compare the Arsenic 0.1
efficiency and unit process design of current wastewater treatment Vanadium 1
Total N 10
technologies for pollutant removal from PRPP wastewater. PRPP
Total P 2
WWTP in Iran was investigated and finally, future perspectives were Sulfide 0.2
discussed. Temperature < 3 at edge of mixing

2. PRPP wastewaters quality and discharge guidelines

There is a long list of organic and inorganic pollutants associated
with PRPP wastewater. Water quality parameters such as oil and grease
(O&G), total hydrocarbon content (THC), total petroleum hydrocarbon
index (TPH-index), biochemical oxygen demand (BOD), soluble BOD
(SBOD), chemical oxygen demand (COD), soluble COD (SCOD), total
organic carbon (TOC), ammoniacal nitrogen, total nitrogen, total sus-
pended solids (TSS), total dissolved solids (TDS), and total metals are
often used as bulk measurements to characterize the water quality.
Special metals such as Cd, Ni, Hg, Pb, and vanadium, specific organics
such as cyanides, phenols, benzene, toluene, ethylbenzene, and xylene
(BTEX), and inorganics such as fluorides, phosphates, sulfides, chlor-
ides, and other micropollutants are also measured in some studies.
General physical parameters include pH (acids, alkalis), hardness, tur-
bidity, heat, taste and odor producers are used in some cases as water
quality indicators [8,25–29]. The literature review and monitoring data
retrieved from PRPP indicate that the quality of the PRPP wastewaters
vary significantly from plant to plant depending on the characteristics
of the crude oil and the process used in the PRPP [30]. Table 1 sum-
marizes the typical range of PRPP wastewater quality parameters [8]
and the effluent discharge guidelines provided by the World Bank
Group (WBG) [8,31].
In addition to the discharging concentration requirements, WBG
guidelines also require that the effluent should not result in a greater
than 3 °C temperature increase at the edge of the mixing zone or 100 m
from the point of discharge for direct dumping to surface waters. These
guideline values are assumed to be achievable under usual PPRP op-
erating conditions using appropriately designed and operated WWTP
facilities through the application of pollution prevention and control
techniques [31,32]. However, practical experience reveals that it has
been increasingly challenging for PRPPs to meet such discharging
guidelines due to the complexity of the PRPP wastewaters.
3. Current PRPP WWTP technologies
Current PRPP WWTP shares many similarities with municipal
WWTP design, including following unit treatment processes:
pretreatment; primary treatment; secondary treatment; and tertiary
treatment or polishing [22,23,26,33,34]. Unique to PRPP WWTP, pri-
mary wastewater treatment include two stages: namely primary oil and
water separation followed by secondary oil and water separation.
American petroleum institute (API) separator, corrugated plate inter-
ceptor (CPI) separator, parallel plate interceptor (PPI) separator, tilted
plate interceptor (TPI) separator, hydrocyclone separators, and buffer
and/or equalization tanks are the most common technologies applied in
the primary oil and water separation. Suites of technologies that share
the similar principal are used in the secondary separation. They include
dissolved air flotation (DAF), dissolved gas flotation (DGF), induced air
flotation (IAF), induced gas flotation (IGF)) [22,23,26,30,33,34]. First
stage oil and water separation is usually applied when oil concentra-
tions in the wastewater exceed ˜500 mg/L. Second stage of primary
treatment is employed to remove small oil droplets and suspended so-
lids, oil emulsions and oil wetted solids that have not been separated in
the first stage of primary treatment [8,30]. A review of technologies
currently used in the treating PRPP wastewater around the world is
presented in Table 2.
In secondary treatment, similar to the principal of municipal WWTP
biological reactor, PRPP WWTP uses microbial activities to consume/
degrade remaining dissolved oil and other organic pollutants [8,12,22].
Microorganisms in the secondary reactor can be either enriched from
naturally occurring microbial communities by the individual treatment
plant or be purchased from commercial vendors to seed in the reactor.
The commercial vendors also provide specific groups of microbial
consortia that have acclimatized to specific organics that are toxic or
recalcitrant to microbial degradation [29]. Over 200 species of bacteria,
yeasts, and fungi have been reported to degrade hydrocarbons ac-
cording to Zobell [62] and Zhu et al. [63]. Hassanshahian and Cappello
[64] reported that 79 bacterial genera, including 9 cyanobacterial
genera, 103 fungal genera, and 14 algal genera can degrade or convert
hydrocarbons.
In secondary bioreactor, dissolved oil and recalcitrant organics are
oxidized into simple end products such as CO2, H2O, and CH4 under
aerobic, anaerobic or semi aerobic conditions. A C:N:P ratio of 100:5:1
has been shown to be optimal for microorganisms growth in bioreactor

2
 Table 2
Technologies and configurations applied in different PRPP WWTPs around the world.
Company
/Location
Refinery of Barrancabermeja-Colombia
PEMEX refinery, Mexico
A Mexican refinery
Chevron refinery, Canada
Marathon petroleum oil refinery, USA
The Frontier oil refinery in Cheyenne,
WY, USA
Amazonas oil refinery, Equador
Lindsey refinery, UK
Humber refinery, UK
3
Porto refinery, Portugal
Kırıkkale TUPRAS refinery, Turkey
A refinery in the western region of
India
Haldia refinery, India
Panipat refinery, India
Bhatinda refinery, India
Gujarat refinery, India
Mangalore refineries & petrochemicals
limited (MRPL), India
Pertamina refinery unit IV, Cilacap,
Indonesia
A refinery in the Philippines
Tehran refinery, Iran
Refinery in southwestern of Iran
Wastewater treatment Sludge treatment Effluent purpose Reference
Oily wastes collection system, API, equalization basin, Gravitational and thermal dehydration using vapor injection, Surface discharge or recycling [35]
neutralization pond, coagulation/flocculation, flotation pond, injection of a polymer followed by centrifugation, biodegradation,
biological phenol removal pond, oxidation and sedimentation and final disposal
S. Jafarinejad and S.C. Jiang
pond
API, DAF, biological process (activated sludge), immersed RO permeate to refinery for reuse and RO [36,37]
reinforced hollow-fiber UF (ZeeWeed® UF system), and RO reject to discharge
membrane
Sumps, equalization, screens, equalization, API, equalization, CPI, Discharge to surface water body, irrigation, [38]
equalization, DAF, oxidation lagoon, stabilization lagoon, and firefighting
activated sludge, sedimentation, chlorination
Sour water stripping, API, DAF, aeration with equalization, Deep Route to the Greater Vancouver Regional [39]
Shaft Technology Inc. (DSTI™) activated sludge bioreactor, District sewer system, where it receives further
dissolved air flotation, clarifier and final effluent polishing by treatment prior to being discharged
biofilters
Screening, equalization, DAF, ZeeWeed MBR system Sludge is thickened in a filter press and then hauled off site Discharge into the City of Ashland’s [40]
wastewater treatment system
API, equalization tank, flash tank, floc tank, bio tank or APS, Sludge from API to sludge thickening tank and sludge from clarifier Discharge to surface water [41,42]
clarifier (In this WWTP, the IFAS process was applied to upgrade to aerobic digester tank
the existing WWTP for better nitrification)
CPI, DAF, activated sludge [43]
API, chemical flocculation or DAF, equalization tank, aerated Discharge to surface water [44]
lagoon, trickling filter, clarifier
Equalization tank, activated sludge unit, water cascade, clarifier, Sludge from clarifier is processed for use as an agricultural Discharge to surface water [44]
holding pond and air flotation unit for final polishing fertilizer
API, PPI, neutralization, coagulation, flotation (DAF), Thickening (gravity thickener), clarification, and final disposal Discharge into the sea or water reuse in the [45]
conventional activated sludge, clarification, chlorination, refinery
mechanical aeration, and filtration
Equalization, Oil separator, flocculation, DAF, activated sludge Thickening and dewatering Discharger into the Kızılırmak river, one of the [46]
process, Sedimentation most important rivers of Black Sea Basin
Sumps, equalization, TPI, flash mixer, coagulation/flocculation, Sludge thickener, dewatering centrifuge, lagoons, and disposal Discharge [47]
DAF or tilted plate flotation tank (TPF), neutralization tank, bio-
tower, intermediate clarifier, activated sludge system or aeration
tank, final clarifier, pressure sand filters and granular activated
carbon (GAC) filters
API, DAF, bio-tower, filtration, high rate contact type clarifier, [48]
and RO plant
TPI, DAF, bio-tower, aeration, clarifier, filtration, pressure sand Gravity thickener and centrifuge [48]
filter, and dual media filter,
Raw wastewater treatment plant, SBR, and MBR Sludge bioremediation [48]
TPI/CPI, DAF, biological treatment by plastic media bio-tower Dewatering of sludge Reuse as makeup to cooling tower [49]
trickling filter and activated sludge process, filtration by PSF and
ACF
API, TPI/CPI, DAF, filtration by DMF and ACF, biological Bioremediation of oily sludge and dewatering. The bioremediation Reuse/recycle [49]
treatment by SBR and MBR. Treated water reuse/recycle systems plant consists of treating thickened oily sludge in a confined batch
consisting of UF and RO membrane units followed by degasser. bioreactor with indigenously prepared microbes for conversion as
bio-sludge that can be transferred to non hazardous land fill sites.
API, CPI, equalization tank, DAF, aeration tank, sedimentation Sludge from aeration tank to belt filter press Discharge [2]
tank, and clean water tank
Pre-separator, DAF, aeration pond, clarifier, impounding basin Discharge to Manila Bay [50]
API, evaporation basin, chemical addition, floatation unit, (Sludge from flotation unit to sludge basin)/(sludge from biological [51]
biological treatment unit, clarifier, chlorination, deep bed treatment unit to sludge treatment, evaporation and/or landfill)
filtration
Oil/water separator, equalization, DAF, secondary treatment Sludge thickening Discharge [52]
(continued on next page)
Journal of Environmental Chemical Engineering 7 (2019) 103326
 Table 2 (continued)
Company
/Location
QP Refinery Mesaieed, Qatar
Dora refinery, Baghdad, Iraq
Kuwait National Petroleum Company
(KNPC)
The refineries in some Middle East
countries
Suez oil processing company (SOPC),
oil refinery in Egypt
SAMIR Refining company
Petroleum refinery at the San Francisco
Bay area
Refinery in the Chicago area
Petroleum refinery located on Taiwan's
southwest Coast
Yokogawa Corporation of America
MARINER plus s.r.o. (Flottweg,
4
Solenis)
Wastewater treatment Sludge treatment Effluent purpose Reference
Equalization tank, flow splitter, CPI, equalization, neutralization, Treated water from EDR is reused to refinery [53]
aeration basin, clarifier, pressure sand filter, activated carbon for cooling tower and rejected water from EDR
filter, and EDR plant is discharged to sea
S. Jafarinejad and S.C. Jiang
API separators, chemical tank, DAF, aeration tank, secondary Sludge thickener, sludge treatment by CaO, O2, and steam Discharge [54]
clarifier, and chlorination
TPI/CPI, DAF, biological treatment by carrousel type activated Dewatering of sludge [49]
sludge process, filtration by continuous flow sand filters
Diversion pit, API separators, equalization tank, DAF, aeration sludge receiving pond, sludge centrifuge, sludge hopper, Discharge to river/sea [55]
basins, clarification, sand filters evaporation pond
API, screw type pump, flash mixing equipment, coagulation/ Sludge dewatering system Discharge to sea [56]
flocculation, chemical preparation and feeding system, DAF, and
air saturation system
Predecanteur, separator, packaging station, aeroflotation, Sludge thickener and sludge treatment Discharge to the sea [57]
aeration, clarifier
(Sour water to stripping, chemical flocculation, activated sludge Discharge [58]
oxidation)/(Desalter brine slop, etc. to primary separations, API,
air flotation unit), aeration, holding pond, submerged diffuser
API, equalization tank, sedimentation tank, activated sludge Centrifuge and landfill Discharge to canal [58]
oxidation, clarifier, chlorination, treated water holding basin, and
multi-cone aerators
CPI, Neutralization tank, DAF, deep activated sludge aeration [59]
tanks A/B/C/D, MBR, and effluent pit
API, DAF, activated sludge treatment/nitrification basin, Sludge thickening, sludge digestion, sludge dewatering, and Discharge [60]
chlorination, and sand filter disposal
Acid/lye, API, flotation, aeration tank, and clarifier (Sludge from API to pretreatment and Flottweg Tricanter)/(sludge Discharge [61]
from clarifier to Flottweg Decanter)
Journal of Environmental Chemical Engineering 7 (2019) 103326
S. Jafarinejad and S.C. Jiang Journal of Environmental Chemical Engineering 7 (2019) 103326

Table 3
Performance of the different biological systems for the treating wastewater effluents from PRPP at industrial scale.
Process Performance References

PACT process COD, BOD, and oil and grease removals for a refinery wastewater were 79.05%, > 95.07%, and 95.27%, [8,68,69]
respectively. Effluent soluble BOD, soluble COD, and oil and grease for a petrochemical wastewater were < 30,
135, and 5 mg/L, respectively.
SBR BP refinery Ltd utilized SBR technology for upgrading of a lagoon system applied for secondary treatment of [12,70,71]
petroleum refinery wastewater during a major expansion of an existing refinery; using a HRT of 36 h and SRT of
40 days the total COD in the petroleum refinery wastewater was decreased to 50-150 mg/L.
MBR WWTP in Marathon petroleum oil refinery, which consists of screening, equalization, DAF, ZeeWeed MBR [40]
system, is able to remove more than 97% of the BOD, 70% of the COD, 90% of the oil and grease, 92% of the
BTEX, and 92% of the TSS present in the wastewater.
IFAS IFAS technology has provided consistently superior treatment efficiency than a conventional activated sludge [41,42]
process. The ammonia removal data has reported a 73% improvement in the IFAS bioreactor with only a small
fill fraction of media.
Aerated lagoon According to Pombo et al. [67], removal efficiencies can be between 80% and 90% for TSS, 65% and 80% for [67,72]
COD, and 50% and 95% for BOD, depending on the type of system. In addition, according to Bush [72], removal
efficiencies can be 75-95% for BOD, 60-85% for COD, 40-65% for suspended solids, 70-90% for oil, 90-99% for
phenol, and 95-100% for sulfides.
Activated sludge 88-95% BOD reduction and 98-99% phenol removal for refinery wastewater; 95-97% BOD removal for [73]
petrochemical wastewater
Deep Shaft Technology Inc. (DSTI™) activated The Chevron refinery WWTP in Burnaby, BC, which consists of a deep shaft bioreactor followed by a DAF [74]
sludge bioreactor clarifier and effluent polishing biofilters, is able to degrade approximately 75% of the COD and 95% of the BOD
present in the wastewater.
Trickling filter The trickling filters from the Lindsey refinery have shown good BOD removal efficiencies (75-100%) but the [44,72]
poorest efficiency of COD removal (28-54%). According to Bush [72], removal efficiencies can be in the range
of 60-85% for BOD, 30-70% for COD, 60-85% for suspended solids, and 50-80% for oil, depending on the filter
type, its loadings, medium type, etc.

[8,12,29]. Amendments are often added to the bioreactor to reach the
optimal C:N:P ratio in order to achieve the best biodegradation activ-
ities. Again similar to municipal WWTP, PRPP WWTP biological
treatment processes can employ diverse technologies including sus-
pended growth processes such as activated sludge process (ASP),
powdered activated carbon treatment (PACT) process, sequencing
batch reactors (SBRs), continuous stirred tank bioreactor (CSTB), and
membrane bioreactors (MBRs). For small scale treatments, attached
growth processes such as trickling filters (TFs), fluidized bed bioreactor
(FBB) and rotating biological contactor (RBC) are also commonly found
in treatment applications [8,12,23,29,65,66]. Hybrid systems that
combine the suspended and attached growth processes are adapted
more recently in order to enhance oil removal efficiencies and improve
effluent quality [29]. A nitrification or a combined nitrification/deni-
trification system can also be adapted to removal high concentration of
ammonia or nitrogen that may be present in some of the PRPP waste-
water [23,26]. Natural treatment through aerated lagoons can also ef-
fectively promote oil degradation [67].
The performance of different biological systems around the world
for treating PRPP wastewater effluent at industrial scale is compared in
Table 3. In general, BOD removal efficiencies can be in the range of
88–97% for activated sludge, > 95.07% for PACT process, > 97% for
MBR, 50–95% for aerated lagoon, 95% for DSTI™ activated sludge
bioreactor followed by a DAF clarifier and effluent polishing biofilters,
60–85% for trickling filter (Table 3).
Among diverse secondary treatment technologies, activated sludge
was the most used option around the world (Table 2). Improved re-
movals of BOD, COD and refractory organics; improved stability to
shock loads and toxic upsets; less tendency to foam in aerator [66,75];
the operational flexibility enhancement of the WWTP [68]; lower ef-
fluent toxicity [69,75]; metals, volatile organic compound (VOC)/odor,
and color control and minimization [68,69]; improved sludge settling
[75] or simplified solids management [69] have generally been listed as
advantages of PACT process over conventional activated sludge (CAS).
SBR technology may promote the mineralization of the wastewater
containing toxic compounds [76]; but it has limited application in the
PRPP WWTP [8,12,23]. MBR technology can successfully be used to
treat PRPP wastewaters, but its application is not common and facing
some challenges such as higher cost-effectiveness. In the petroleum
industry, where further tertiary treatment such as reverse osmosis (RO)
is required, MBR can be preferred to the other option of using media
filtration and microfiltration after biological treatment [8,23]. It is
anticipated that the application of MBR technology in the PRPP WWTPs
will be increased with decreasing the membrane cost [8,77]. DSTI™
activated sludge bioreactor has had limited application in PRPP WWTP
[39]. Because of the current stringent effluent standards for PRPP,
aerated lagoons are used less frequently for wastewater treatment
[8,23]. When a high-quality discharge is not required, TF may be used
in refineries and/or it may also be applied upstream of an ASP to treat
wastewater [8,49,72].
Regardless of the technology employed in the secondary treatment,
the performance of secondary treatment can be affected by different
factors, including wastewater flow and quality, aeration rate, food/
microorganism (F/M) ratio, sludge loading, sludge volume index (SVI),
sludge age or sludge retention time (SRT), mixed liquor suspended
solids (MLSS), and wastewater temperature [29]. In addition, SBR
performance may be affected by organic loading rate, hydraulic re-
tention time (HRT), SRT, DO, and influent characteristics such as COD,
solids content, C/N ratio [78,79].
Orbecido et al. [80] assessed and contrasted aerobic biological
treatment methods including CAS, SBR, IFAS, and MBR for a petroleum
refinery WWTP with respect to three criteria: i) economic including the
capital and operating cost; ii) environmental including the treated ef-
fluent quality, ability to adjust to hydraulic and contaminant loading,
ability to answer oil entry, and land footprint; iii) technical including
the need of pretreatment and secondary clarifier, reliability and validity
of systems, and complexity to perform and control. Their results de-
monstrated that SBR was the most precedent option followed by CAS.
The sensitivity analysis indicated that the ranking of the alternative
treatment technology weighed heavily by the economic and environ-
mental aspects of the technology [80]. Jafarinejad [81] studied the
performance and economics of CAS process replacing by SBR tech-
nology in a full-scale two train petroleum refinery WWTP using com-
puter simulation. He reported that under the design criteria and op-
erational conditions used in the study, the treated effluent investigated
parameters from both petroleum refinery WWTPs containing CAS +
CAS and SBR + CAS processes complied with the regulated treated
effluent standards and the energy and amortization costs for both plants

5
S. Jafarinejad and S.C. Jiang
were higher in comparison with the operation, maintenance, material,
and chemical costs [81].
Tertiary treatment or polishing step, which takes place downstream
of the secondary treatment is traditionally achieved through sand fil-
tration, activated carbon filtration [22,23,33,34,72], or chemical oxi-
dation [23,34,72]. More recently membrane separation technologies
including ultrafiltration (UF) [8,26,33] and RO [26] have been applied
to PRPP wastewater treatment to improve the effluent quality for dis-
charge or reuse [34]. Other advanced treatment technologies including
ion exchange, electrodialysis (ED) and electrodialysis reversal (EDR)
are proposed and applied in small scale applications. Advanced oxida-
tion processes (AOPs) using hydrogen peroxide/ultraviolet (H2O2/UV),
ozonation process, Fenton and photo-Fenton, heterogeneous photo-
catalysis, electrochemical oxidation, wet air oxidation (WAO) and su-
percritical water oxidation (SCWO) have also been proposed or tested
in laboratory to remove recalcitrant chemical pollutants to discharge or
reuse requirement. However, most of the advanced processes have not
been employed in the industrial scale PRPP WWTP [8,23].
3.1. PRPP WWTP design and configurations
Fig. 1 shows a typical PRPP wastewater treatment system that in-
cludes equalization, primary and secondary oil/water separation, bio-
logical treatment, biological or secondary clarification, tertiary treat-
ment and solids handling [8,82,83]. Equalization system is applied to
smooth out fluctuations or variations in flow and composition of the
wastewater influent [23,72,82] in order to minimize potential spikes in
loads to the downstream processes. Flow equalization reduces the size
of the downstream units and the cost of the overall WWTPs. Con-
centration equalization minimizes contaminant shock loading to the
bioreactor [8,23]. Studies show equalization significantly improves the
effectiveness of biologically-based system [8,72]. Equalization system
may be located upstream of the primary oil/water separation (API se-
parator) [23], upstream of the secondary oil/water separation (the
DAF/IAF) [23,72,82], or downstream of the secondary oil/water se-
paration (the DAF/IAF) [23,82] as illustrated in Fig. 1. If upstream of
the API separator is selected for the location of equalization system, due
to the separation tendency of oil and solids contained in the oily was-
tewater in this tank, hardware (piping/pumps and controls) should be
supplied for the elimination of free oil and solids from the tank to
prevent accumulation of these materials. Equalization system must be
cleaned once or twice a year depending on the solids and oil content of
Fig. 1. A typical PRPP wastewater treatment system (modified from [8,82,83]).
6
Journal of Environmental Chemical Engineering 7 (2019) 103326
the oily wastewater [8,23].
Wastewater segregation and/or segregated wastewater treatment in
the petroleum refineries is beneficial for improving treatment efficiency
and reuse of treated water. Such practice is especially important in
water-scarce regions, yet it is not commonly practiced. Segregation may
be based on the total dissolved solids (TDS) content of the wastewater
to separate into: 1) Low TDS water including stripped sour water,
stormwater, and miscellaneous wastewater; and 2) High TDS water
including desalter effluent, tank bottom sediment and water (BS&W),
and spent caustic. Fig. 2 illustrates a segregated wastewater treatment
system that includes two parallel trains with the identical unit opera-
tions except the step of primary oil/water separation. An API separator
is not needed for the low TDS train due to the low suspended solids
content of the wastewater [8,23].
As already shown in Table 2, PRPP WWTPs’ technologies and con-
figurations can vary from plant to plant. Three simplified process flow
diagrams (PFDs) of TUPRAS petroleum refinery WWTP (Fig. 3), PEMEX
refinery WWTP (Fig. 4), and Barrancabermeja-Colombia refinery
WWTP (Fig. 5 (a) for wastewater treatment section and Fig. 5 (b) for
oily sludge treatment section) are presented as examples of diverse
design. There have not been direct comparisons of the treatment effi-
ciencies and effluent water quality for diverse technologies and design
configurations amongst different PRPPs around the world.
3.2. PRPP WWTP in Iran
Iran is one of the largest producers and exporters of petroleum
(crude oil and natural gas) in the world and the National Iranian Oil
Company (NIOC) is one of the world’s largest oil and gas companies by
proven reserves [8]. There are many PRPPs in Iran which large quan-
tities of wastewaters are generated from their activities and processes
that must be treated [84].
The simplified PFD of a refinery WWTP for the oily wastewater in
Iran is shown in Fig. 6. The purpose of this refinery WWTP is to process
the refinery wastewater to meet the quality for surface discharge to
evaporation pond and to recycle the treated effluent for the use as
cooling towers make-up water [81]. The plant has been designed to
process and/or treat waste streams of desalter oily water, oily water
sewer, oily water from sour water stripper, non-oily water sewer and
sanitary sewer. The wastewater influent is first separated by two API
separators into two equalization basins. The waste stream flowing into
two DAF units is treated by H2SO4 or NaOH for pH control, followed by
S. Jafarinejad and S.C. Jiang Journal of Environmental Chemical Engineering 7 (2019) 103326

Fig. 2. Segregated wastewater treatment system (modified from [8,23]).

Fig. 3. The simplified process flow diagram of TUPRAS petroleum refinery WWTP in Turkey (modified from [46]).

Fig. 4. The simplified process flow diagram of PEMEX refinery WWTP in Mexico (modified from [36]).

7
S. Jafarinejad and S.C. Jiang
Fig. 5. The simplified process flow diagram of wastewater treatment section (a) and oily sludge treatment section (b) of Barrancabermeja-Colombia refinery WWTP
(modified from [35]).
coagulant dosing with polyelectrolyte and mixing through a static
mixer. A secondary coagulant aid such as ferric chloride is then added
in the DAF and oily scum is scraped off from the surface to return to oily
sludge thickener. Nutrients including P and Urea are amended in the
waste stream entering the two aeration basins, each equipped with four
mechanical aerators for biological treatment. The mixed liquor is then
flowed into two clarifiers, which then send sludge to an aerobic digester
and supernatant to filter units. Disinfection of the secondary effluent is
achieved through injection of chlorine from chlorination units. Total
organic carbon (TOC) is monitored continuously in-stream of the final
effluent to provide feed back as if the water quality is sufficient for
reuse in cooling tower or to divert the effluent to the evaporation pond
if quality does not meet cooling tower makeup specifications. The fil-
tration may also be reprocessed through DAF to improve water quality
for cooling tower reuse.
The sanitary sewage (not shown in Fig. 6) consists of two lines, each
Fig. 6. The simplified process flow diagram of a refiner WWTP in Iran for the oily wastewater.
8
Journal of Environmental Chemical Engineering 7 (2019) 103326
one composed by a comminutor, an equalization basin, an aeration
basin, a clarifier basin, a chlorine contact chamber. The tertiary treat-
ment unit consists of three solid accumulation chambers, three dual
filter basins, a clear water storage chamber and two effluent chambers.
The storm-water is recovered in a basin, skimmed to remove floatable
oil, and sent to the main treatment downstream API separators. The
desalter oily water effluent is routed through two oil/water separators
before it joins the oily process water upstream of the equalization ba-
sins.
In the most PRPP WWTPs in Iran, the treatment purpose is the
compliance with the regulations set by regulatory agencies. Due to the
water scarcity in Iran, water reuse issue must be the driving force for
the PRPPs to treat wastewaters with suitable treatment technologies.
On the other hand, among diverse secondary treatment technologies,
activated sludge is the most used option in PRPP WWTPs in Iran. Thus,
advanced treatment technologies should be implemented to make
S. Jafarinejad and S.C. Jiang
wastewaters suitable for reuse. In addition, Iranian petroleum industry
and researchers should pay more attentions to the commercialization of
innovative processes and designs, computer modeling and simulation of
PRPP WWTPs behavior for process optimization, modernization and
modification to plant configuration, energy saving, and implementation
of instrumentation, control and automation methods.
4. Advancements in PRPP WWTPs and future trends
Continues development of technology in PRPP WWTP is necessary
to keep pace with the increase in demand of petroleum products, ex-
haustion of high quality oil reserve, heightened environmental aware-
ness among human society and stricter discharge regulations focusing
on environmental protection. Such new technology developments
should base on the past PRPP WWTP design and operation experience
and the specific local conditions. The new technologies should con-
tribute to fundamental shift of mentality from wastewater discharge to
recycle and reuse within the industry. The new technologies should also
include on-line monitoring and smart feedback loop to ensure effluent
water quality for environmental protection and decisions for retreat or
reuse.
PACT system designed by Siemens Water Technologies [85] is an
example of new technology for PRPP wastewater treatment. This
system, recently adapted by China Petroleum & Chemical Corporation
(Sinopec Corp.) at Anqing refinery in Anhui Province, China, combines
biological treatment and carbon adsorption into a single, synergistic
treatment step to remove organics. The post treatments include a
Zimpro wet air regeneration (WAR) hydrothermal unit and a hydro-
clear sand filtration system to increase the finishing water quality. A
first membrane based PRPP wastewater treatment plant was designed,
constructed and operated by General Electric (GE) in 2012. The ad-
vanced GE ZeeWeed UF and Mobile RO are used for a petroleum
company of Trinidad & Tobago Ltd (PETROTRIN) in the West Indies
[86]. In 2014, a Russian oil company Bashneft took an additional step
to incorporate GE's ZeeWeed MBR, EDR and RO technologies for the
treatment of refinery wastewater from the Bashneft-Ufaneftekhim oil-
processing complex and other enterprises of the Northern Industrial
Block of Ufa [87]. The membrane-based technologies are likely to be-
come more common in the future years because of their dramatic im-
provements in effluent water quality to meet the requirement for reuse
and environmental protection [88]. The recent advancements in
membrane permeability and antifouling property make them attractive
options in upgrading the PRPP WWTP. However, wastewater treat-
ments are cost centers in refineries - they aren't profit centers. As such,
PRPP WWTPs frequently don't have sufficient resources to implement
technology improvement with significant impact on the financial
bottom line. These departments often struggle trying to get financial,
manpower, and interdepartmental support from the finished product
departments.
To balance the cost of technology improvement in WWTP and fin-
ishing water quality requirement for reuse, future trends in designing
and constructing of WWTPs for the PRPP should focus on hybrid
technologies to improve the treatment capacity and pollutant removal
upon existing technology without the significant increase in design and
operational cost. There is a great potential for PRPP wastewater treat-
ment to incorporate membrane separation technologies such as MBR as
additional treatment trains due the compact size of membrane systems
in comparison with bioreactors [89]. Furthermore, forward osmosis
(FO) that separates water from salt and organics with minimal energy
requirement and low membrane fouling propensity may become an
energy efficient option for oily wastewater treatment with reduce op-
erational cost [90,91]. Advanced oxidation processes (AOPs) have also
been proposed for removal of toxicity and recalcitrant organics in the
effluent of treated PRPP wastewater. The final selection of treatment
technologies should consider the balancing of economic, environmental
and technical suitability and regulatory constraints.
9
Journal of Environmental Chemical Engineering 7 (2019) 103326
5. Conclusions
Oil companies are among largest companies in the world. They are
also the largest water consumers of the world. Extreme pressures exist
to improve upon environmental considerations and to reduce or opti-
mize operating costs. Technology enhancement in PRPP wastewater
treatment is the best approach to achieve both goals through reduction
of environmental impact and reuse the water for product generation.
The existing PRPP WWTP around the world treats oily influent through
primary treatment, secondary treatment, and tertiary treatment or
polishing. However, the design and configuration of the plants are
highly diverse and regional specific. With the increase of petroleum
products, water scarcity and stricter environmental regulations, new
technologies to improve the PRPP wastewater treatment efficiency and
effluent water quality that fit for reuse are needed. Amongst diverse
technologies that are being explored, membrane separation shows po-
tential own to its relatively low cost and significant improvement in
effluent water quality. Finally the selection of PRPP wastewater treat-
ment technology should balance the economic, environmental and
technical suitability and regulatory constraints.
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgments
Financial support from DOE U.S.- China CERC-WET is acknowl-
edged.
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