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Evaluation of a three-step process for the treatment of petroleum refinery wastewater

Muftah H. El-Naas *, Manal Abu Alhaija, Sulaiman Al-Zuhair

Chemical and Petroleum Engineering Department, UAE University, P.O. Box 15551, Al-Ain, United Arab Emirates


Article history: In this study, a novel three-step process was developed and evaluated for the treatment of highly contaminated refinery
Received 29 July 2013 Accepted 25 wastewater. The process consisted of an electrocoagulation cell (EC), a spouted bed bioreactor (SBBR) with
November 2013 Pseudonymousputida immobilized in polyvinyl alcohol gel, and an adsorption column packed with granular activated carbon
produced from agricultural waste, specifically date pits. The units were evaluated individually and as combinations with
different arrangements at different operating conditions to treat refinery wastewater with varying levels of contaminants. The
Keywords: EC unit was found to be effective as a pretreatment step to reduce the large concentrations of COD and suspended solid and
Petroleum refinery wastewater reduce the load on the bioreactor and the adsorption column. At optimum conditions and unit arrangement, the process was
Electrocoagulation able to reduce the concentration of COD, phenol and cresols by 97%, 100% and 100%, respectively. The process was found to
be highly competitive in comparison with other combined systems used in the treatment of industrial wastewater and can handle
highly contaminated refinery or industrial wastewater with relatively wide range of operating conditions.
2013 Elsevier Ltd. All rights reserved.

Introduction In petroleum and petrochemical industries, there is strong interest in

improving wastewater management by optimizing water use and introducing
With the remarkable economic growth envisaged in the world nowadays, recycling technologies in production units. In general, refinery wastewater
concerns are raised about many environmental challenges. In petroleum and contains many and diverse contaminants, several inorganic substances, such as
petrochemical industry, more than 2500 useful petroleum products are produced Mg2+, Ca2+, S2, Cl, and SO42 that upgrade the mineralization of water; emulsified
from crude oil [1] and the annual worldwide consumption of petroleum oil and grease, phenols, cresols, sulfides, ammonia and cyanides contribute to
hydrocarbons is estimated to be approximately 1012 US gallons [2]. Depending the chemical oxygen demand (COD). As a result, an effective approach should
on the size, type of crude oil, products and complexity of operation, a petroleum be developed to face stringent environmental regulations on the quality of
refinery can be a large consumer of water and can generate significant volumes effluent discharged for recycling purposes [6]. Table 1 summarizes the main
of wastewater. The estimated average water consumption in processing a barrel pollutants in different petroleum refining units.
of crude oil is 6590 gallon (246341 L) [3]. Approximately 0.41.6 times the The traditional treatment of refinery wastewater is based on
volume of the processed crude oil is discharged as petroleum refinery physicochemical, mechanical methods and further biological treatment in the
wastewater [4]. Thus, based on the current yield of 84 million barrels per day integrated activated-sludge treatment unit. Several solutions are proposed
(mbpd) of crude oil, a total of 33.6 mbpd of effluent is generated globally [5]. including electrocoagulation [1,7,8], photocatalytic oxidation [9], wet oxidation
World oil demand is expected to rise to about 107 mbpd over the next two [10], photodegradation [11], catalytic vacuum distillation [6], coagulation
decades, and oil will account for 32% of the worlds energy supply by 2030 [5]. flocculation [12,13], fenton oxidation [14], adsorption [15,16], biodegradation
These data clearly indicate that effluents from the oil industry will continually [17], membrane [18] and membrane bioreactor [1921], ultrasound [22] and
be produced and discharged into the worlds main water bodies. chemical precipitation [23]. However, because of the variability of refinery
wastewater composition, the traditional methods become inadequate and could
not be used individually in full scale. So, there is still a need for advanced
techniques to remove non-biodegradable, high concentration organic substance
of petroleum refinery wastewater [10]. In other words, researchers are
attempting to design a combination of
* Corresponding author. Tel.: +971 3 713 5188; fax: +971 3 713 5188.
E-mail address: (M.H. El-Naas).
2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved.
Table 1
Major water sources in petroleum refining process [3].
Unit Wastewater main pollutants

Crude desalting Free oil, ammonia, sulfides and suspended solids

M.H. El-Naas et al. / Journal of
Environmental Chemical Engineering 2 (2014) 5662 57
Crude oil distillation Sulfides, ammonia, phenols, oil, chloride, mercaptans
Thermal cracking H2S, ammonia, phenols
Catalytic cracking Oil, sulfides, phenol, cyanide, ammonia
Hydrocracking High in sulfides
Polymerization Sulfides, mercaptans, ammonia
Alkylation Spent caustic, oil, sulfides
Isomerization Low level of phenols
Reforming Sulfide
Hydrotreating Ammonia, sulfides, phenol

Table 2
Characteristics of refinery wastewater samples as ranges of values.
Parameter Value

pH 8.38.9
Conductivity (mS/cm) 5.26.8
Total suspended solid (g/l) 0.030.04
Total dissolved solid (g/l) 3.86.2
SO4 (mg/l) 14.516
COD (mg/l) 36005300
Total phenol (mg/l) 160185
Phenol (mg/l) 1114
o-Cresol (mg/l) 1416.5
m,p-Cresol (mg/l) 7275
N-hexane (mg/l) 1.81.85

treatment methods for a complete and successful removal of such pollutants. microwaveassisted catalytic wet air oxidation [10] were investigated for
Although biological treatment and bioremediation techniques are well refinery wastewater treatment.
established for the clean-up of petroleum contaminated land and wastewater In this study, a combination of an electrochemical process, a biological
[11], there is a need for enhancement of enzymatic capacity of the employed treatment with a spouted bed bioreactor (SBBR) and an adsorption fixed bed
microbial communities. An improvement can also be achieved by column packed with granular activated carbon was evaluated for the treatment of
pretreatment technologies, to decrease the priority pollutants concentration as refinery wastewater. The integrated three-step system was tested under different
much as possible before the biodegradation step. Several solutions are operating conditions and the experimental results obtained for the optimized
proposed including the use of coagulants and electrochemical oxidation system were compared with those reported in the literature for similar processes.
[13,24], fenton oxidation [25], electron-beam [26], ozonation [27].
In recent years, there has been increased interest in the application of
electrocoagulation in the treatment and purification of industrial wastewater Experimental methods
[28]. Electrocoagulation is efficient in removing suspended solids as well as
oil and greases. It removes metals, colloidal solids and particles, and soluble Wastewater characterization
inorganic pollutants from aqueous media by introducing highly charged
polymeric metal hydroxide species. These species neutralize the electrostatic Refinery wastewater samples were obtained from a petroleum refinery and
charges on suspended solids and oil droplets to facilitate agglomeration or were preserved in dark, plastic containers. Analyses of the samples are given as
coagulation. Because of the many advantages for this technique, ranges of values in Table 2.
electrocoagulation has been suggested widely as one of those advanced
alternatives used as a pretreatment step for industrial wastewater treatment. A Bacterial suspension
combination between EC and TiO2 photocatalysis was applied for the
reduction of COD from pharmaceutical and cosmetic industries wastewater A special strain of the bacterium Pseudonymous putida was obtained in a
[29]. 90% of COD reduction was achieved after the EC process. Linares- cereal form (AMNITE P 300) from Cleveland Biotech Ltd., UK. A 100 g of the
Hernandez et al. found a complete elimination of COD by combining EC cereal was mixed in a 1 L of 0.22% sodium hexametaphosphate buffered with
with electrooxidation [30]; whereas, 84% COD reduction efficiency was Na2CO3 to a pH of 8.5. The mixture was homogenized in a blender for about one
achieved using EC biosorption process [31]. EC was also combined with a hour, decanted and kept in the refrigerator at 4 8C for 24 h. Bacteria slurry was
biological treatment used for winery wastewater [32]. prepared by first low speed centrifugation at 6000 rpm (4508 g) for 15 min. Then,
Combinations of different treatment techniques were recommended for the the supernatant was collected and centrifuged again at 10,000 rpm (12,522 g) for
treatment of highly contaminated industrial wastewater. Ultrafiltration with 20 min. The centrifugation was carried out using IEC CL31R Multispeed
electrocoagulation [33] and advanced oxidation with biodegradation [34] Centrifuge, Thermo Electron Cooperation, USA. Harvested bacteria cells were
were suggested for the treatment of olive mill wastewater with COD reduction collected and kept in the refrigerator for immobilization. Nutrients mineral media
efficiency of about 96% and 91%, respectively. ECirradiation treatment was was prepared according to Table 3.
another combination used in the treatment of highly colored and polluted
industrial wastewater with COD reduction of about 95% [35]. Chemical Immobilization of bacteria in PVA gel
coagulation, electrochemical oxidation and biological treatment were used as
a combination for the treatment of bactericide [24] and textile wastewaters Polyvinyl alcohol (PVA) gel was used for immobilizing the bacteria cells as
[36]. Leather industry [37] and integrated dyeing [25] wastewaters were also reported in a previous study [41]. A homogenous 10 wt% PVA viscous solution
treated using biological and fenton oxidation process. Jung et al. [38] was prepared by mixing 100 g of PVA
suggested the combination between adsorption and microfiltration membrane
bioreactor for advanced tertiary wastewater treatment. Pre-oxidation, co- Table 3
Composition of nutrient mineral media.
precipitation, adsorption and coagulation were used as a combined process for
Component Concentration (g m3)
the treatment of high arsenic content industrial wastewater [39]. A
combination of PACs and coagulant with ultrafiltration [40] and MgSO47H2O 300
M.H. El-Naas et al. / Journal of Environmental Chemical Engineering 2 (2014) 5662
K2HPO4 250 were carbonated and activated to produce DP-AC. The carbonization was
CaCl22H2O 150 performed in a tube furnace (Thermolyene, USA) which was initially purged with
(NH4)2CO3 120 a flow of nitrogen for 10 min. After that, the furnace was heated at a rate of 10
FeSO47H2O 3.5
8C/min up to 600 8C and then kept at this temperature for 4 h.
ZnSO47H2O 1.3
CoCl26H2O 0.015 After cooling to room temperature, the material is considered carbonized, but
Na2MoO42H2O 0.013 still inactive. After weighing the inactive carbon, it was activated in the same
tube furnace at a temperature of 900 8C using a flow of carbon dioxide instead
58I[(ig._1)TD$FG] of nitrogen. The resulting AC was then degassed under vacuum (Shel Lab,
USA) for about 2 h before use [15].

Experimental setup

Refinery wastewater samples were treated using the integrated system

shown in Fig. 2. The wastewater was pumped to the 1500 ml cylindrical
electrocoagulation reactor (14 cm in diameter and 6 cm height) using
peristaltic pump (GILSON Mini plus 3) with a flow rate of 10 ml/min. The
aluminum plate electrodes (4 cm 6 cm 1 mm) were dipped into the
wastewater and connected to a DC power source (POPULAR PE-23005) to
provide a current of 0.1 A (current density of 3 mA/cm2) and a voltage of
about 17 V; the voltage depends on the conductivity of the wastewater. The
distance between the anode and the cathode was kept constant at 7.5 cm. The
effluent from the electrocoagulation unit was sent to a settling tank, where the
overflow was pumped to the spouted bed bioreactor (SBBR). The spouted bed
bioreactor was made of Plexiglas with a total volume of 1.1 L and was
equipped with a surrounding jacket for temperature control. Detailed
Fig. 1. SEM photo for immobilized bacteria in PVA.
description of the SBBR can be found elsewhere [43,44]. The temperature of
the reactor system was controlled by circulating water into the reactor jacket
from a water bath set at the desired temperature. Air was continuously
introduced through the bottom of the reactor at a flow rate of 3 L/min to
powder with 900 ml of distilled water at about 7080 8C. PVA is a synthetic
enhance mixing and at the same time provide excess oxygen to sustain aerobic
polymer that has better mechanical properties, and it is more durable than Ca-
conditions. The reactor was initially filled with standard nutrient media
alginate which is biodegradable and can be subject to abrasion [42]. The formed
containing 30 vol% PVA gel cubes with immobilized bacteria. The
mixture was allowed to cool to room temperature before adding 10 ml of the
temperature of the water bath, and hence the reactor system, was set at 30 8C.
bacterial suspension prepared as in Bacterial suspension section, then well stirred
This temperature was found to be the optimum in a preliminary runs which
for 1015 min to ensure homogeneity of the solution. The solution was then
also agrees with previous studies in the literature [45]. The product from the
poured into special molds and kept in a freezer at 20 8C for 24 h, then transferred
bioreactor was then fed to the adsorption column, which was made of a
to the refrigerator and allowed to thaw at about 4 8C. The freezingthawing
Plexiglas column (50 cm in length and 3 cm inside diameter). The column was
process was repeated 3 4 times, with 5 h for each cycle. The frozen molds were
packed with 130 g of granular activated carbon. More details about the
cut into 1 cm3 cubes, washed with distilled water to remove any uncrosslinked
adsorption kinetics and equilibrium data as well as the regeneration of the
chains, and sent for acclimatization as per the procedure described in [41]. Fig. 1
saturated activated carbon can be found elsewhere [15,16]. At regular
shows the distribution of immobilized bacteria in PVA.
intervals, samples were collected from the effluent of each treatment unit and
analyzed for COD and phenol concentrations. All experiments were carried
Date pits activated carbon
out at room temperature.
Date pits activated carbon (DP-AC) was prepared from raw date pits granules.
The granules were washed, dried, grinded and screened. The collected granules

Fig. 2. A schematic diagram of the integrated system. (1) Feed tank, (2) feed pump, (3) electrocoagulation reactor, (4) magnetic stirrer, (5) DC power supply, (6) settling tank, (7) pump, (8) biological
reactor, (9) adsorption column and (10) product tank.
M.H. El-Naas et al. / Journal of Environmental Chemical Engineering 2 (2014) 5662 59


Liquid flow rate: 10 ml/min

The electrocoagulation unit, spouted bed bioreactor and adsorption adsorption column then the concentration increases with time as the activated
column were connected in series with different configurations and operated carbon gets saturated.
continuously for the treatment of real refinery wastewater, which had a dark
greenish color and a strong, pungent odor, with initial concentrations ranging Electrocoagulationbiodegradationadsorption arrangement
from 3600 to 5300 mg/l and 11 to 14 mg/l for COD and phenol, respectively.
The samples withdrawn after each treatment unit were analyzed for their COD Figs. 5 and 6 show the effluent concentrations of COD and phenol at steady
content and phenol concentrations as a function of time. Table 4 summarizes state conditions for electrocoagulation and after 24 h of operation for both
conditions used in the experiment for each treatment unit. biodegradation and adsorption systems. The results show that the
electrocoagulation unit reduced the COD concentration by about 46%. The
Electrocoagulationadsorptionbiodegradation arrangement bioreactor further reduced the feed contaminants, which came from the
electrocoagulation step, by about 73% for COD, 61% for the phenol.
In this section, results for the arrangement of electrocoagulation Nevertheless, most of the reduction in COD and other phenols has taken place in
adsorptionSBBR are shown for the reduction of COD and phenol for about the adsorption unit, where the final cumulative reduction reached 97% and 100%
3 h. Fig. 3 shows the COD reduction after each treatment unit, with the for COD and phenol, respectively. The final effluent after the adsorption column
electrocoagulation pretreatment step contributing 46% to the overall reduction had COD and phenol concentrations within the acceptable discharge limits. A
of COD. However, the reduction percentage increased to about 83% by summary of the complete system results is shown in Table 5, where after the last
passing the effluent through the adsorption column. The effluent from the treatment step the effluent showed almost complete reduction for phenols and
adsorption is sent to the bioreactor, where the COD reduction is very low 97% reduction for COD content.
compared to the electrocoagulation and adsorption stages. The cumulative To demonstrate the effectiveness using a combination of electrochemical
COD reduction after the biodegradation increased to only 85%. It is worth process, biological treatment using SBBR and
noting here that the adsorption column reached the saturation after the third
hour which increased the load on the SBBR and consequently decreased the
efficiency of the overall treatment process. ig._5)T$FIGD[(]
Fig. 4 shows the reduction of phenol concentration for this system. There
is no significant reduction in phenol concentration in the electrocoagulation
unit, but a very high reduction occurs in the adsorption column which initially
reduces the phenol concentration to zero in the first 3 h after the feed enters
the g._3)D$FIG]T[(i

Treatment Step
Fig. 5. The COD concentration after each treatment step for the refinery wastewater in
electrocoagulationbiodegradationadsorption system.
Treatment Step

Fig. 3. The COD concentration after each treatment step for the refinery wastewater in
electrocoagulationadsorptionbiodegradation system.
Feed EC Adsorption SBBR

Treatment Step
Fig. 4. Phenol concentration after each treatment step for the refinery wastewater in
electrocoagulationadsorptionbiodegradation system.
M.H. El-Naas et al. / Journal of Environmental Chemical Engineering 2 (2014) 5662
technology. Electrocoagulation reduced the contamination of the refinery
wastewater by 46% and 34% for COD and phenol, respectively. Meanwhile,
passing refinery wastewater through the packed bed of activated carbon
showed a reduction of 65% and 85% for COD and phenol. However, the
activated carbon was saturated after only 8 h of operation. On the other hand,
97% reduction for COD and a complete reduction of phenol were achieved
when using the three units in series for a longer operating time of 24 h, giving
a clear indication that this combination can be considered to be the most
efficient unit arrangement and as one of the most effective alternatives for the
treatment of refinery wastewater.

Treatment Step
Fig. 6. Phenol concentration after each treatment step for the refinery wastewater in
electrocoagulationbiodegradationadsorption system.

Table 5
Summary of the results of ECSBBRAD treatment system.

pH 7.2 9.1 7.8 8.2 8.2 8.2

Conductivity (mS) 5.4 6.2 6.2 6.73 6.73 8.24
TSS (g/l) 0.072 0.244 0.11 0.17 0.05 0.01
TDS (g/l) 3.38 3.6 3.6 4.03 4.03 4.95
COD (mg/l) 4190 2267 2267 1116 1116 110
Phenol (mg/l) 12.2 8.1 8.1 4.8 4.8 0
m,p-Cresol (mg/l) 75 64 64 33 33 0

adsorption for treating refinery wastewater, results were compared to the

percentage reduction for both COD and phenol after the treatment of such
wastewater using the same continuous treatment units individually. Fig. 7 shows
that biological method

Table 6

Ph en ol





Treatment Setup
Fig. 7. Comparison for the percentage reduction of COD and phenol after individual unit
treatment and the three units in series.

could not be used as an individual treatment unit for the refinery wastewater
treatment as a pretreatment step is needed in conjunction with this sensitive
M.H. El-Naas et al. / Journal of Environmental Chemical Engineering 2 (2014) 5662 61
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