Removal of Polycyclic Aromatic Hydrocarbons (PAHs) from Offshore

Produced Water using Advanced Oxidation Processes (AOPs)

Bing Chen*, Baiyu Zhang**, L. Jing, B. Liu, J.S. Zheng, Y.C. Ma

* NRPOP Lab, Faculty of Engineering and Applied Science, Memorial University of Newfoundland, St. John’s,
NL, Canada A1B 3X5, bchen@mun.ca
** NRPOP Lab, Faculty of Engineering and Applied Science, Memorial University of Newfoundland, St.
John’s, NL, Canada A1B 3X5, bzhang@mun.ca

Abstract: Owing to the stringent environmental regulations imposed in recent years, the disposal of produced
water becomes an important issue to both the operator and the marine environment. Yet current treatment
practices mainly focus on physical removal where dissolved hydrocarbons are not effectively treated. In this
study, 16 EPA polycyclic aromatic hydrocarbons (PAHs) spiked in offshore produced water were treated by
using nano-TiO2 enhanced photodegradation, ozonation and ultrasound/ozonation. The results demonstrated that
PAHs in produced water can be effectively removed by using advanced oxidation processes (AOPs).

Keywords: PAHs, Produced water, AOPs, Photodegradation, Ozonation

Introduction
Produced water represents the largest volume waste stream associated with offshore oil and
gas exploration and production. Current conventional treatment technologies are mostly
gravity-based separation where dissolved organic compounds particularly polycyclic aromatic
hydrocarbons (PAHs) would remain unaffected (de Bruyn et al. 2012). To sort out this
situation, it is much desired to employ advanced secondary treatment technologies. Such
urgent needs can be accomplished by using advanced oxidation processes (AOPs) (Jing et al.
2013). In this study, the aforementioned AOPs were applied and investigated in destructing
PAHs from offshore produced water.

Material and Methods

Produced water samples were received from offshore platforms in Atlantic Canada. 16-PAH
standard solution was purchased from Agilent. Dichloromethane and Acetone were purchased
from Honeywell Burdick and Jackson. TiO2 powder (anatase) was purchased from Sigma
Aldrich and Aeroxide P25 nano-scale TiO2 was purchased from Fishersci. Ozone generator
was purchased from Yanco Industries Ltd. Ultrasound generator was purchased from
BRANSON Ultrasonics Corporation, USA. (1)
For nano-TiO2 enhanced photodegradation experiments, produced water (500 ml) was first
spiked with 100 μl of 10 μg/ml 16-PAH standard solution in a 1-L reactor jar. Catalyst was
added to form 0.10 g/L slurry solutions. The slurry solutions were vigorous stirred for 30 min
before irradiation to achieve equilibrium. The mixed solution was then irradiated by a high-
pressure mercury lamp (UVP, 8 W) with a peak of 254 nm (3.7 mw/cm2) at the top of the jar.
The ozonation experiments were conducted in a 1L column with bubble diffuser. The flow
rate of ozone inlet was 250 ml/min oxygen with 10 μg/ml ozone. The samples collected
before and after treatment were prepared by spiking 1 μg 16 PAHs in 1 L produced water.
For ultrasound assisted ozonation experiments, 16-PAH standard solution (1 ml at 10 μg/ml)
was spiked into produced water (700 ml) and stirred for 15 minutes. Ozone was injected from
the bottom of the jar and its flow rate was maintained at 10 μg/mL O2. The ultrasonic power
of the tip-type is 450 W at 50% amplitude. All water samples collected from different
experiments were pre-treated and analyzed by GC-MS (Liu et al. 2013).

Results and Conclusions

From Table 1, it can be seen that the photocatalytic degradation of PAHs followed the first
order reaction. PAHs with smaller molecular weights tended to have higher rate constants
than those with higher molecular weights. Due to the low UV intensity, turbidity could act as
a key factor that inhibited the degradation process. The results also showed that ozonation
alone was capable of achieving high removal rates of PAHs, ranging from 65% to 99.7% in
60 minutes (Figure 1.1a). In addition, the ultrasound-assisted ozonation process can further
promote such efficiencies up to 98% in 60 minutes (Figure 1.1b). These results suggested that
the use of AOPs prior to the final disposal of produced water can help the industries to
comply with the stringent environmental standards.
Table 1.1 The first order reaction rate constants (k) of the TiO2 photocatalytic oxidation of 16 EPA PAHs

NAP ANY ANA FLU PHE ANT FLT PYR

k (min-1) 6.46E-4 0.0018 9.25E-4 0.0012 3.72E-4 0.0029 1E-4 2.50E-4

BaA CHR BbF BkF BaP DBA BPY IPY

k (min-1) 3.67E-4 1.32E-4 1.22E-4 1.52E-4 5.78E-4 1.82E-4 N/A 1.77E-4

12 NAP BaA
(a) (b) ANY CHR
10 ANA BbFA
Relative concentration of PAHs

FLU BkF
PHE BaP
8
ANT IPY
FLT BPE
6 PYR DBA

0 10 20 30 40 50 60
Time, min

Figure 1.1 The removal process of 16 PAHs by using (a) ozonation and (b) ultrasound-assisted ozonation

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