Journal of Environmental Sciences 2010, 22(12) 18751882

Treatment of oileld produced water by anaerobic process coupled with micro-electrolysis

Gang Li1,2 , Shuhai Guo1, , Fengmei Li1
1. Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, China. E-mail: ligang@iae.ac.cn 2. Graduate School of Chinese Academy of Sciences, Beijing 100039, China Received 26 January 2010; revised 23 April 2010; accepted 12 June 2010

Abstract Treatment of oileld produced water was investigated using an anaerobic process coupled with micro-electrolysis (ME), focusing on changes in chemical oxygen demand (COD) and biodegradability. Results showed that COD exhibited an abnormal change in the single anaerobic system in which it increased within the rst 168 hr, but then decreased to 222 mg/L after 360 hr. The biological oxygen demand (ve-day) (BOD5 )/COD ratio of the water increased from 0.05 to 0.15. Hydrocarbons in the wastewater, such as pectin, degraded to small molecules during the hydrolytic acidication process. Comparatively, the eect of ME was also investigated. The COD underwent a slight decrease and the BOD5 /COD ratio of the water improved from 0.05 to 0.17 after ME. Removal of COD was 38.3% under the idealized ME conditions (pH 6.0), using iron and active carbon (80 and 40 g/L, respectively). Coupling the anaerobic process with ME accelerated the COD removal ratio (average removal was 53.3%). Gas chromatography/mass spectrometry was used to analyze organic species conversion. This integrated system appeared to be a useful option for the treatment of water produced in oilelds. Key words: heavy oil produced water; anaerobic system; micro-electrolysis; biodegradability DOI: 10.1016/S1001-0742(09)60333-8

Introduction
Produced water, which is generated in the exploitation processes of oil and gas industries, is the largest waste stream source found in oilelds. Nowadays, more-stringent environmental standards have led to greater eorts being made to treat produced water. Many technologies have been developed for the removal of petroleum pollutants and chemical oxygen demand (COD), including otation (Ebrahimi et al., 2010), membrane separation (Qiao et al., 2008; C akmakcea et al., 2008), chemical precipitation (Doyle and Brown, 2000; Carvalho et al., 2002; Zhou et al., 2000), chemical oxidation (Bessa et al., 2001), and biological treatment (Lu et al., 2009; Li et al., 2005; Zhao et al., 2006). Among these technologies, biological treatment is frequently used for the treatment of oileld produced water because of its high eectiveness and economical feasibility. Many laboratory- and pilot-scale experiments have been performed under aerobic conditions, such as stabilization ponds (Shpiner et al., 2009), biological aerated lter (Su et al., 2009), sequencing batch reactor (SBR) systems (Freire et al., 2001). Nevertheless, because the biological oxygen demand (ve-day) (BOD5 )/COD ratio is relatively low in oileld produced water, it is dicult to decrease COD
* Corresponding author. E-mail: shuhaiguo@iae.ac.cn

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using a single aerobic biological technology. Therefore, anaerobic processes have become increasingly popular for the treatment of produced water with two aims: (1) to catalyze the hydrolysis of organic compounds into longchain fatty acids, and (2) to improve the degradability of the produced water. Anaerobic processes are feasible for the treatment of high-strength wastewater (McHugh et al., 2003), converting organic pollutants to small molecules in various non-biodegradation wastewaters (Barker et al., 1999). Heavy oil produced water is, however, dicult to degrade (Guo et al., 2002), because it contains large quantities of large-molecule non-biodegradation organics. Low BOD5 /COD ratios and long processing time are potential problems associated with such anaerobic treatments. Therefore, it is necessary to improve the biodegradability of produced water and optimize the anaerobic treatment conditions. Many methodologies have been employed previously to improve the biodegradability of produced water, including Fenton process, oxidation with ozone and micro-electrolysis (ME). Among them, ME method is costeective and operationally simple (Wang et al., 2004; Shen et al., 2001; Nurul Amin et al., 2008). ME is an electrochemical process involving an active carbon cathode and an iron anode. The following half reactions occur at the

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electrodes: Iron anode (oxidation): Fe 2e Fe2+ , E 0 (Fe2+ /Fe) = 0.44 V Active carbon cathode (reduction): 2H+ + 2e H2 , E 0 (H2+ /H2 ) = 0 V (2) (1)

Most investigations into ME have indicated that the zero-valent iron can reductively transform electronwithdrawing constituents, making previously recalcitrant compounds more amenable to the subsequent biological oxidation process (Bell et al., 2003; Jin et al., 2003). Therefore, we suspected that ME methodology might provide a convenient model system for the improvement of the biodegradability of produced water. The objectives for this study were to determine the eect of a single anaerobic process on the organics species present in produced water and to determine the eciency of treating produced water through a combination of anaerobic processing and ME. Particular attention was paid to investigating the conversion and removal of organics in oileld produced water.

Fig. 1 Schematic representation of the experimental apparatus used for the treatment of oil produced water. (1) pump; (2) ME operation reactor; (3) anaerobic reactor; (4) table-ap; (5) heat isolating materials; (6) overow weir.

1 Materials and methods

1.1 Raw produced water and materials Raw produced water was collected from a heavy oil produced water plant located in the Liaohe Oileld, Liaoning Province, northeastern China. The wastewater was treated with the intrinsic processes of oil separation and otation, providing a mean COD 274 mg/L. Table 1 lists several chemical parameters of this wastewater sample.
Table 1 Parameter pH Temperature (C) COD (mg/L) BOD5 (mg/L) Mineral oil (mg/L) Chemical parameters of the produced water sample Value 7.4 0.3 32 4 274 16 16 4.7 56.7 4.2 Parameter TOC (mg/L) SS (mg/L) TN (mg/L) TP (mg/L) Value 136 5.8 72 12.9 12.5 2.4 0.11 0.04

Metal) were added. The iron pieces were cut to a diameter of ca. 1 mm and a length of 15 mm, with irregular shape. They were degreased in a 10% hot alkaline solution, then soaked in a 2% H2 SO4 to remove surface rusts; and nally washed three times with deionized water. The clean iron was dried naturally. Activated carbon (industrial grade, Liaoning Province, China) was used as a macroscopic electrode material having a diameter of ca. 2 mm and a height of 10 mm, with a columnar shape. In order to eliminate adsorption eects, the active carbon was saturated with raw wastewater for 24 hr prior to use. NaOH (2 mol/L) and H2 SO4 (1 mol/L) solutions were used to adjust pH. All chemical reagents used in the experiments were analytical grade and obtained from Shenyang Chemical Reagent Corporation. 1.3 Experimental procedure and design The produced water was rst treated in the sequencing batch anaerobic reactor through Path A. The experiment was conducted to study the removal of organic species in a single anaerobic reactor. The treatment period was set as 15 days. Next, an experiment was performed to investigate the COD removal and biodegradability of the produced water in the anaerobic process coupled with ME, through Path B. The anaerobic reactor was seeded with anaerobic sludge from a full-scale anaerobic pond at the produced water plant with volatile suspended solid (VSS) concentration of 25 g/L. The reactor was started using produced water at a desired temperature, and pH 7.2. No nutrients were added in the anaerobic system. During the adaptive phase, COD of the inuent was maintained in the range 260300 mg/L at a constant hydraulic retention time (HRT) of 360 hr in the anaerobic reactor. When COD removal rate of the integrated system was stable, the inuent concentration was maintained relatively constant (average COD: 274 mg/L). The system was operated for three periods, with the pH, COD, BOD5 , and TOC measured routinely. For ME process, the experiments were rstly performed in beakers to determine the optimal parameters. Pretreated iron and active carbon were added to beakers at various dosage ratios. Wastewater (1 L) was then added into each beaker and mixed. During the reaction process, an agitation

1.2 Performance of reactor system A semi-hermetic, rectangular (length, 0.4 m; width, 0.3 m; height, 0.4 m) anaerobic bioreactor was constructed to treat the produced water continuously on a laboratory-scale. The sequencing batch reactors were made of stainless steel consisting of two parts (Fig. 1): one is ME operation unit and the other is an anaerobic process unit. The working volumes of the two reactors were 6 and 30 L, respectively. The produced water could be pumped into the two reactors independently (Path A and Path B, respectively). A table-ap was set up in the anaerobic unit. The whole reactor was packed using heat isolating materials. In ME unit, industrial cast iron lings and shavings, that were mainly free of visible rust (Shenyang Institute of

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apparatus with six agitators that rotated simultaneously at the same speed (JJ-4A Jiangsu Province, China), was used under insucient oxygen as soon as practically possible. Each batch experiment lasted for 8 hr. At designed intervals, the supernatant was removed and kept still for 60 min prior to analysis, and the dosage of active carbon was 40 g/L, and the dosage of iron was 20, 40, 80 or 100 g/L. The initial pH was adjusted from 4.0 to 9.0 to determine the optimal reaction condition. The experiments for determining the parameters were conducted in a water bath at 32C for determining the parameters. For anaerobic process coupled with ME (Path B), the pH of the inuent was adjusted to 6.0 to facilitate the ME reaction. The appropriate HRT was employed in ME. The wastewater treated through ME was then collected in the anaerobic reactor; its pH was adjusted to the same value as that used for anaerobic treatment. The treatment parameters in Path B were identical to those in Path A. pH, COD, BOD5 , and TOC were measured routinely. 1.4 Analytical methods Prior to analysis, the supernatant sample was ltrated through 0.45-m lter paper. All analytical procedures were performed according to standard methods. COD was measured using the potassium dichromate oxidation method. BOD5 were determined using the ve-day BOD test method (APHA, 1999). TOC was analyzed using a TOC analyzer (TOC-500, Shimadzu). The content of hydrocarbons in the produced water was measured using gravimetric methods (Wei et al., 1998; Reddy and Quinn et al., 1999; Huang et al., 2003). Alkyl, aromatic, pectin, and bitumen samples were separated and measured using methods described previously (Wang et al., 2009). Gas chromatography/mass spectrometry (GC/MS) was used to analyze of organic compounds in pretreated samples that had been subjected to liquid-liquid extraction using CCl4 (chromatogram pure grade, Fisher Corporation, USA). The extraction procedure was conducted under acidic, neutral, or alkaline conditions (Cao et al., 2007). Pretreated samples (1 L) were analyzed using a Trace MS Trace 2000GC/MS system (Finnigan, USA). Highly pure He (99.999%) was used as a carrier gas (ow rate: 1 mL/min). A DB-5MS capillary column (inner diameter: 0.25 mm; length: 30 m) was adopted in the separation system. The temperature for the gasication compartment was maintained at 260C. The temperature control program for the column involved maintaining the temperature at 90C for 1 min and then increasing it to 300C at an increment of 5C/min. The electron energy and the electron double voltage were set at 70 eV and 1200 V, respectively. The molecular weights were scanned from 90 to 900 Da.

addition, the composition of hydrocarbons was analyzed to investigate the changes in the levels of organics after single anaerobic treatment. 2.1.1 Removal and conversion of organic matter during single anaerobic process Figure 2 displays the dynamic changes in COD and BOD5 after treatment in the single anaerobic system. The COD of the inuent was 274 mg/L, a typical value for heavy oil produced water. In the steady state, the mean COD of the sample underwent a continuous increase within the rst 168 hr of the experiment, reaching 341 mg/L (a 24.5% increase). After 168 hr, the COD of the produced water decreased gradually. After 360 hr of operation, the COD of the euent was less than 222 mg/L. Almost 18.9% of the COD was removed during the entire process. BOD5 exhibited a similar trend. Within the rst 144 hr of the anaerobic process, the BOD5 increased from 16 mg/L to a maximum concentration of 52.3 mg/L. After 360 hr, the BOD5 transmission was 22.6 mg/L. Although we observed similar trends for COD and BOD5 , the range of COD value exceeded that of BOD5 . In addition, the time required to reach the maximum COD lagged behind that of BOD5 . The maximum BOD5 /COD ratio of 0.15 was achieved after 144 hr. Under anaerobic conditions, increased COD value was observed for heavy oil produced water, which contrasts with other refractory organic wastewater treatment systems. The present results can be explained by considering that some contaminants in the raw oil water might not be oxidized by the COD method used in this study. Whereas, after anaerobic processing, they were degraded into simpler components that could be measured using the potassium dichromate oxidation process. (1) Straight-chain carboxylic acids may have been completely oxidized, but the aromatics and polynuclear aromatics are not readily oxidized, even in the presence of a catalyst (Ag2 SO4 ); (2) pectin in the raw produced water may have been oxidized only partially, whereas fatty acids derived from pectin through biotransformation during the anaerobic process might be oxidized during the potassium dichromate oxidation process. The relationship between COD and theoretical oxygen demand (ThOD) has been investigated for several specic classes of organic chemicals (Baker et al., 1999). In this study, however, the

2 Results

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COD, BOD5 , and TOC were measured to evaluate the removal of organics by the single anaerobic process. In

Fig. 2 Dynamic change of COD and BOD5 during the single anaerobic process.

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2.1 Eect of anaerobic process on oileld produced water

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COD obtained reects the presence of only some organic compounds; that is, the measured COD was lower than the real quantity of organic compounds. In the anaerobic processing of the heavy oil produced water, two reactions occurred simultaneously: (1) biodegradable organic species were degraded, causing the COD to decrease, and (2) refractory large-molecule organic species were hydrolyzed into simpler compounds, causing the COD to increase. The nal COD was determined from the sum of these two processes. We found that the second reaction was dominant during the rst 168 hr. After then, the rst reaction became dominant and the COD decreased gradually. As shown in Fig. 2, the increase of BOD5 was signicant during the period of anaerobic treatment from 96 to 192 hr; that is, the period of the increase in BOD5 lagged behind that of the COD. This situation arose presumably because the organic species were hydrolyzed slowly within the rst 96 hr, causing BOD5 to increase slowly. The majority of large-molecule organic species were hydrolyzed after 96 hr. The anaerobic process appeared to improve the biodegradability of the wastewater organic species; this hypothesis could be explained by the partial conversion of COD to BOD5 . TOC is believed to be a better indicator for the organic content of wastewater (El-Rehaili, 1995; Visco et al., 2005). As shown in Fig. 3, the TOC content decreased slowly from 136 to 124 mg/L during the rst 168 hr of the experiment. After 360 hr, the nal TOC of the euent stream was 82 mg/L. These ndings suggest that the decrease in TOC can more accurately reect the degradation of the organic contaminants. Within the rst 168 hr of the anaerobic process, since the hydrolysis of pectin predominated in this system, the rate of decrease of the TOC was slow. After 168 hr, the degradation of the organic species was performed predominantly by the anaerobic microorganisms, thus the decrease rate of TOC was accelerated. As a result, the observed changes in COD, BOD5 , and TOC were consistent during the anaerobic process. 2.1.2 Analysis of hydrocarbon group content in anaerobic processes Figure 4 displays the eect of anaerobic treatment on the content of hydrocarbons. The system exhibited an overall

hydrocarbon waste removal eciency of 29.5% (calculated by weight), similar to the total COD removal eciency. The changes in the hydrocarbon group content in anaerobic processes are due to the synergetic actions of anaerobic microorganisms. The contents of alkanes, aromatics, and pectin in the raw wastewater were 31.6, 8.5, and 13.2 mg/L, respectively. The levels of the alkanes and aromatics in the euent after 360 hr were decreased by 18.7% and 14.1%, respectively. The removal of pectin was high (60.6%) during the rst 168 hr, and low (11.4%) thereafter. The content of bitumen barely changed during the entire anaerobic process. The results in Fig. 4 indicate that the transformation of pectin to medium-length and long-chain fatty acids improved the BOD5 and biodegradability to some extent. 2.2 Additional ME process 2.2.1 Eect of dosages of iron and active carbon Figure 5 displays the removal eciencies of COD as a function of reaction time in the presence of various dosages of iron and active carbon at pH 6.0. Overall, the removal eciencies of COD in the wastewater exhibit similar trends. With active carbon of 40 g/L, the removal eciencies of COD at iron dosages of 20, 40, and 60 g/L were 21.6%, 31.4%, and 32.5%, respectively, within a reaction time of 8 hr. When the dosage of iron exceeded 80 g/L, the removal rate of COD increased dramatically. Notably, we observed no obvious additive eect when employing a higher dosage. At 100 g/L, the removal eciency of COD remained at 38.5% after 8 hr. It can be concluded that a transition exists in the ME process at an iron dosage between 80 and 100 g/L. Because an excess of iron would aect the mass transfer eciency, a dosage of 80 g/L would be preferable. Therefore, the optimal ratio of iron to active carbon was 2:1 (W/W ). Increasing the retention time caused the removal eciency of the COD to increase as a result of the formation of macroscopic electrodes. We observed little enhancement upon increasing retention time (Fig. 5). When the reaction was 4, 6, and 8 hr, the COD removal eciencies with optimum iron and active carbon dosages were 33.2%, 34.2%, and 37.6%, respectively. The greater retention time did not improve the eciency dramatically. Taken

Fig. 3

Dynamic change in the TOC during single anaerobic process.

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Fig. 4 Composition of hydrocarbons in the heavy oil produced water during the single anaerobic process.

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biological treatment. The greater removal of COD in this case was due to both chemical reactions and adsorption eects being involved. In addition, the decrease in TOC during the 4 hr ME process was also signicant, but not as great as that of COD. The BOD5 /COD ratio increased from 0.05 to 0.17. Thus, ME has the ability to alter the molecular structures of dissolved compounds, resulting in the increase in wastewater biodegradability. Particular, the ME process produced compounds of lower molecular weight that are more biodegradable.
Table 2 Eects of ME on heavy oil produced water BOD5 (mg/L) 16 28.6 BOD5 /COD ratio 0.05 0.17 TOC (mg/L) 136 104

COD (mg/L) Fig. 5 COD removal as a function of reaction time in the presence of various amounts of iron, active carbon with 1 L wasterwater. Inuent Euent 274 169

together, we considered the optimal retention time as 4 hr. 2.2.2 Eect of initial pH of produced water Figure 6 reveals that the ME process was more eective under acidic conditions. When the initial pH decreased, the removal eciency of COD increased dramatically. After 8 hr, the COD removal eciencies at pH 4.0, 5.0, 6.0, and 7.0 were 40.3%, 37.2%, 36%, and 29.3%, respectively. Higher eciency might be expected for the ME process performed under acidic conditions, partially because of the accompanying coagulation process. On the other hand, the ME technique diers from coagulation because the former involves redox processes. The electrical potential energy between the anode and cathode was enhanced when pH decreased in the reaction system. Extremely low pH, however, is not suitable for anaerobic system. Therefore, the optimal pH for ME process was in the range 5.06.0. 2.2.3 Enhanced biodegradability of produced water in ME process Table 2 lists data reecting the eects of ME on heavy oil produced water. For HRT of 4 hr and pH of 6.0, the COD and TOC decreased by 38.3% and 23.5%, respectively. As expected, the COD of the produced water was eectively eliminated through ME treatment. The behavior of the COD here is dissimilar to that observed for the

2.3 Eect of anaerobic process coupled with ME 2.3.1 Removal and conversion of organic matter by anaerobic process coupled with ME In the system of anaerobic process coupled with ME, the HRT of ME treatment and anaerobic treatment were 4 and 360 hr, respectively. Figure 7 displays the changes in COD and BOD5 in the reactor. The mean COD increased slowly from 169 to 184 mg/L during the rst 96 hr, then decreased slowly. After 360 hr, the COD in the euent was 138 mg/L. Therefore, ca. 18.3% of the COD was removed during the anaerobic process. As a result, the total removal of COD in the system combining the anaerobic process with ME was 49.6%. The BOD5 exhibited a similar trend. The initial BOD5 of the euent after ME processing was 28.6 mg/L. After 120 hr of anaerobic treatment, the BOD5 increased to a maximum concentration of 41.3 mg/L. The BOD5 /COD ratio in the euent varied from 0.17 to 0.22. After 360 hr, the decrease in the content of biodegradable organics resulted in a nal BOD5 /COD ratio of 0.14. Thus, most of the organic compounds were removed when using the integrated system; that is, the biodegradability of the produced water was improved through pretreatment with the ME system. Although many of the organic components in produced water are non-biodegradable, the redox processes

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Fig. 6 COD removal at various initial pH values of raw produced water during the ME process. Iron: 80 g/L; active carbon 40 g/L; wastewater: 1 L; temperature: 32C.

Fig. 7 Dynamic changes in COD and BOD5 during the anaerobic process after ME treatment. Iron: 80 g/L; active carbon: 40 g/L; temperature: 32C; HRT for ME treatment: 4 hr.

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1880 Table 3 Number Peak 1 Peak 2 Peak 3 Peak 4 Peak 5 Peak 6 Peak 7 Peak 8 Peak 9 Identication of peaks using GC/MS Number Peak 10 Peak 11 Peak 12 Peak 13 Peak 14 Peak 15 Peak 16 Peak 17

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Identied compound C14 H22 O3 C15 H24 O C16 H30 O4 C16 H30 O4 C15 H22 O2 C16 H22 O4 C20 H30 O4 C18 H24 O2 C23 H38 O2

Identied compound C29 H48 O2 C18 H24 O2 C17 H36 C16 H22 O4 C35 H72 C30 H50 C28 H42 O4 C29 H50 O

occurring during the ME stage caused some refractory organic compounds to be transformed or removed and other organic compounds to become water-soluble. Furthermore, the biodegradability of euent was also enhanced, increasing the BOD5 and the BOD5 /COD ratio. Therefore, ME is an appropriate method for enhancing the biodegradability of heavy oil produced water. 2.3.2 GC/MS analysis We used GC/MS to analyze the raw inuent and the euent from the anaerobic process coupled with ME (Tellez et al., 2005; Middleditch, 1984). The GC/MS chromatogram of the organic species extracted from the heavy oil produced water was extremely complex. In Fig. 8a, the 17 major peaks having the greatest areas are marked with the largest as peak 10. Figure 8b displays the chromatogram obtained for euent from the anaerobic process coupled with ME. The content of large-molecular substances (e.g., peaks 12, 14, and 15) had been reduced, consistent with the trend for BOD5 . These large molecules had been transformed into smaller ones through hydrolysis in the anaerobic system. A mass of the small-molecule substances were biodegraded (e.g., peaks 1, 2, and 5), consistent with the decrease in TOC. Furthermore, we performed mass spectrometric analyses to identify the 17 main petroleum-based compounds (Table 3). The contents of high molecular weight compounds, such as those represented by peaks 5, 10, 11, 12, and 14, decreased by an average of 37% after anaerobic treatment. 2.3.3 Eciencies of the integrated system Figure 9 displays the changes in COD in the euent of the ME and integrated systems during continuous processing for 45 day. The CODs of the two systems remained steady at ca. 185 and 133 mg/L, respectively, with average COD removal eciencies of 35.4% and 53.3%, respectively, during the operation period. The anaerobic reactors coupled with ME were ecient at removing organic compounds, suggesting that an integrated system featuring anaerobic process coupled with ME might be suitable for the purication of oileld produced water.

Fig. 8 GC/MS analyses of organic contaminants in the raw inuent (a) and euent (b) of the anaerobic process coupled with ME.

Fig. 9 COD variation in the raw inuent and the euent from the single ME and integrated system.

3 Discussion
Earlier publications have reported that the oil-in-water emulsied heavy oil is dicult to be biodegraded (Wu et al., 2003; Zhao et al., 2006). It is dicult to treat the oil wastewater through conventional biological treatment

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system mainly due to slow biodegradability. Surface ow constructed wetland and anaerobic baed reactor (ABR) systems have been used to treat heavy oil produced water with high concentrations of salts and low levels of nutrients (Ji et al., 2007, 2009). In contrast, there are few reports regarding the changes in COD during the anaerobic processing of heavy oil produced water. In this study, we observed an unexpected initial increase in COD during anaerobic treatment, due to refractory organic species being transformed into small degradable organic compounds, primarily through hydrolysis. Lu et al. (2009) demonstrated that, for a strictly anaerobic process, the

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inuent COD content is generally transformed into volatile fatty acids (VFA), alcohol, hydrogen, and biomass; the overall COD content, however, should remain unchanged. Although anaerobic processing is usually designed as the pre-treatment system for aerobic processing (Chan et al., 2009; Tellez et al., 2002), heavy oil produced water is not suited for aerobic treatment because of its low BOD5 /COD ratio. Therefore, anaerobic processes have been designed with longer HRT and lower COD loading (Guo et al., 2002), with the main purpose of enhancing the BOD5 /COD ratio. Anaerobic process has a shortage of long HRT. In general, additive methods are used to enhance the anaerobic eect. ME processing is being used increasingly for COD removal, particularly for refractory organics remediation (Wei et al., 2001). Zero-valent iron is a strong reducing agent that can reductively transform relatively oxidized pollutants, including chlorinated solvents, metals, nitrates, and explosives. We were interested in examining pretreatment with iron as a means to reductively transform electron-withdrawing moieties and render recalcitrant compounds more amenable to subsequent oxidation processes. In this study, we found that 80 g/L of iron and 40 g/L of active carbon were the optimal dosages at a retention time of 4 hr. The optimal pH range for ME process was 5.06.0. We suspect that the parameters are dierent from others wastewater due to the hydrocarbon content in heavy oil. Meanwhile, it should be noted that ME process was in favor of enhancing biodegradability of produced water. In addition, the euent COD concentrations and the corresponding removal eciencies in the reactor were gratifying when coupling the anaerobic and ME processes. The combined method led to a signicant decrease in the content of refractory organic species. This phenomenon suggests that the integrated system is suitable for the treatment of produced water in oilelds.

authors wish to thank the Ministry of Science and Technology, China, for partially funding this study.

References
APHA (American Public Health Association), AWWA (American Water Works Association), WEF (Water Environment Federation), 1999. Standard Methods for the Examination of Water and Wastewater (20th ed.). Washington DC, USA. Barker D J, Mannucchi G A, Salvi S M L, Stuckey D C, 1999. Characterisation of soluble residual chemical oxygen demand (COD) in anaerobic wastewater treatment euents. Water Research, 33(11): 24992510. Baker J R, Milke M W, Mihelcic J R, 1999. Relationship between chemical and theoretical oxygen demand for specic classes of organic chemicals. Water Research, 33(2): 327334. Bell L S, Devlin J F, Gillham R W, Binning P J, 2003. A sequential zero valent iron and aerobic biodegradation treatment system for nitrobenzene. Journal of Contaminant Hydrology, 66(3-4): 201217. Bessa A E, SantAnna Jr G L, Dezotti M, 2001. Photocatalytic/H2 O2 treatment of oil eld produced waters. Applied Catalysis B: Environmental, 29: 125134. C akmakcea M, Kayaalpb N, Koyuncu I, 2008. Desalination of produced water from oil production elds by membrane processes. Desalination, 222: 176186. Cao Z L, Chen J F, Feng Y M, Wang X W, Xu W H, 2007. Study on the treatment of stick oi1 wastewater by hydrolytic acidication-biological contact oxidation process. Industrial Water Treatment, 27(1): 6668. Carvalho M S, Clarisse M D, Lucas E F, Barbosa C C R, 2002. Evaluation of the polymeric materials (DVB copolymers) for produced water treatment. In: SPE International Petroleum Exhibition and Conference. Abu Dhabi, UAE. 1316. Chan Y J, Chong M F, Law C L, Hassell D G, 2009. A review on anaerobic-aerobic treatment of industrial and municipal wastewater. Chemical Engineering Journal, 155(1-2): 1 18. Doyle D H, Brown A B, 2000. Produced water treatment and hydrocarbon removal with organoclay. In: SPE Annual Technical Conference and Exhibition. Dallas, Texas, USA. 14. Ebrahimi M, Willershausen D, Shams Ashaghi K, Engel L, Placido L, Mund P et al., 2010. Investigations on the use of dierent ceramic membranes for ecient oil-eld produced water treatment. Desalination, 250(3): 991996. El-Rehaili A M, 1995. Response of BOD, COD and TOC of secondary euents to chlorination. Water Research, 29(6): 15711577. Freire D D C, Cammarota M C, SantAnna G L, 2001. Biological treatment of oil eld wastewater in a sequencing batch reactor. Environmental Technology, 22(10): 11251135. Guo S H, Bai Y X, Zhang H R, Sun T H, Qu J H, 2002. Study on pre-treatment process of super viscous oil emulsion wastewater. Research of Environmental Sciences, 15(1): 1 4. Huang N X, Ma H R, Wang X R, Feng J F, Ding P, 2003. GC analysis of petroleum hydrocarbons in soil and water samples contaminated by crude. Journal of Shaanxi University of Science & Technology, 21(6): 2529. Ji G D, Sun T H, Ni J R, 2007. Surface ow constructed wetland for heavy oilproduced water treatment. Bioresource Technology, 98(2): 436441.

4 Conclusions
We have experimentally investigated the removal of organic species from heavy oil produced water through single anaerobic treatment and the coupling of anaerobic processing with ME. In the single anaerobic system, the COD and BOD5 both increased initially over time and then decreased gradually. The BOD5 /COD ratio of the produced water increased upon treatment. The organic composition changed during anaerobic processing. Coupling anaerobic treatment with ME accelerated the conversion and biodegradation processes. GC/MS analysis revealed that combined treatment was particularly eective for the conversion of large-molecule organics to smaller ones that were biodegraded only partially. Thus, the combined process was very eective at transforming most of the organic pollutants found in the heavy oileld produced water. Acknowledgments This work was supported by the Water Pollution Control and Management Project, China (No. 2009ZX07208). The

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Ji G D, Sun T H, Ni J R, Tong J J, 2009. Anaerobic baed reactor (ABR) for treating heavy oil produced water with high concentrations of salt and poor nutrient. Bioresource Technology, 100: 11081114. Jin Y Z, Zhang Y F, Li W, 2003. Micro-electrolysis technology for industrial wastewater treatment. Journal of Environmental Sciences, 15(3): 334338. Li Q X, Kang C B, Zhang C K, 2005. Waste water produced from an oileld and continuous treatment with an oil-degrading bacterium. Process Biochemistry, 40: 873877. Lu M, Zhang Z Z, Yu W Y, Zhu W, 2009. Biological treatment of oileld-produced water: A eld pilot study. International Biodeterioration & Biodegradation, 63: 316321. McHugh S, OReilly C, Mahony T, Colleran E, OFlaherty V, 2003. Anaerobic granular sludge bioreactor technology. Reviews in Environmental Science and Biotechnology, 2: 225245. Middleditch B S, 1984. Ecological Eects of Produced Water Discharges from Oshore Oil and Gas Production Platforms (1st ed.). American Petroleum Institute, Washington DC. Nurul Amin M D, Kaneco S, Kato T, Katsumata H, Suzuki T, Ohta K, 2008. Removal of thiobencarb in aqueous solution by zero valent iron. Chemosphere, 70: 511515. Qiao X L, Zhang Z J, Yu J L, Ye X F, 2008. Performance characteristics of a hybrid membrane pilot-scale plant for oileld-produced wastewater. Desalination, 225: 113122. Reddy C M, Quinn J, 1999. GC-MS analysis of total petroleum hydrocarbons and polycyclic aromatic hydrocarbons in seawater samples after the north cape oil spill. Marine Pollution Bulletin, 38(2): 126135. Shen Z M, Wang W H, Jia J P, Ye J C, Feng X, Peng A, 2001. Degradation of dye solution by an activated carbon ber electrode electrolysis system. Journal of Hazardous Materials, B84: 107116. Shpiner R, Liu G, Stuckey D C, 2009. Treatment of oileld produced water by waste stabilization ponds: Biodegradation of petroleum-derived materials. Bioresource Technology, 100: 62296235.

Su D L, Cong L, Wang J L, Zhou D, 2009. Treatment of oil-eld produced water by combined process of anaerobic baed reactor (ABR)-biological aerated lter (BAF): a pilot study. International Journal of Environment and Pollution, 38: 12. Tellez G T, Nirmalakhandan N, Gardea-Torresdey J L, 2002. Performance evaluation of an activated sludge system for removing petroleum hydrocarbons from oileld produced water. Advances in Environmental Research, 6: 455470. Tellez G T, Nirmalakhandan N, Gardea-Torresdey J L, 2005. Comparison of purge and trap GC/MS and spectrophotometry for monitoring petroleum hydrocarbon degradation in oileld produced waters. Microchemical Journal, 81: 12 18. Visco G, Campanella L, Nobili V, 2005. Organic carbons and TOC in waters: an overview of the international norm for its measurements. Microchemical Journal, 79: 185191. Wang Y G, Yang J F, Ke H, 2004. Treating oily wastewater of oil eld by electro-Fenton method. Journal of Yangzhou University (Natural Science Edition), 7(4): 7982. Wei F S, 1998. Standard Method for the Examination of Water and Wastewater. Environmental Science Press of China, Beijing. Wei J, Zhou J, Shao J, 2001. Experiment study on treating chemical industry wastewater containing chlorbenzens by microcell electrolysis process. Journal of Chemical Engineering, 15(1): 4952. Wu B F, Shen B X , Yang Y M , 2003. A study on viscosity reduction of Liaohe super-heavy crude oils through emulsication in water. Oileld Chemical, 20(4): 377379. Zhao X, Wang Y M, Ye Z F, Borthwick A G L, Ni J R, 2006. Oil eld wastewater treatment in biological aerated lter by immobilized microorganisms. Process Biochemistry, 41: 14751483. Zhou F S, Zhao M F, Ni W X, Dang Y S, Pu C S, Lu F J, 2000. Inorganic polymeric occulent FMA for purifying oileld produced water: preparation and uses. Oileld Chemical, 17: 256259.

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