Factors influencing the aggregation behavior of residual associative polymer in produced oily fluids
Abstract
The influence of emulsified oil, suspended solids, Fe3+, Fe2+, cationic water clarifier and sulfate-reducing (SR) bacteria on the aggregation behavior of residual hydrophobic modified polyacrylamide in treated oily wastewater from polymer flooding was studied by fluorescence spectroscopy and dynamic light scattering. The result of I 1 /I 3 showed that the polarity of hydrophobic microdomains increased, whereas the size of the hydrophobic microdomains may be decreased, where the value of I 1 /I 3 represents the ratio of the intensity of peak I 1 (374.0 nm) to that of peak I 3 (385.0 nm) of the vibration fine structure of pyrene monomer emission in residual polymer solution. The results of the ratio of I 1 at 48 h to I 1 at 0 h (I 1,48h /I 1,0h) indicated that oil and cationic water clarifier could inhibit the aggregation to some extent, while Fe2+ and suspended solids were helpful for aggregation, and Fe3+ and SR bacteria had no significant influence on the aggregation of polymer.
Keywords
Aggregation behavior Fluorescence spectrum Residual polymer in treated water Hydrophobic modified polyacrylamide1 Introduction
Polymer flooding plays a major role in global crude oil recovery (Wever et al. 2011), and this process can enhance oil recovery by 12% compared with water flooding (Shen et al. 2005; Xu et al. 2010; Lin et al. 2008). In recent years, polymer flooding has been widely used in major oil fields of China, such as Daqing and Shengli Oilfields (Gao et al. 2011; Shi et al. 2010, 2012; Feng et al. 2009; Zhang and Yue 2008; Zhang et al. 2008). One of the most widely used water-soluble polymers is partially hydrolyzed polyacrylamide (HPAM), which controls mobility in reservoirs by increasing the viscosity of the injected water, and more importantly, by reducing the permeability of the formation (Lu et al. 2012; Ren et al. 2006; Guo et al. 2014; Lin et al. 2011). Usually, there is residual polymer in treated oily wastewater produced from polymer flooding (TOWPF) (Yang et al. 2014; Li et al. 2012; Lei et al. 2008). TOWPF can be used for reinjection or polymer flooding (Qu et al. 2014; Liu et al. 2010). In addition, there were many other substances in the TOWPF, such as emulsified oil, suspended solids, Fe3+, Fe2+, cationic water clarifier and sulfate-reducing (SR) bacteria. These substances have great influence on the stability of residual polymer. If the polymer is not stable, then it might aggregate and sediment in the buffer vessel, thereby affecting the reinjection process. Therefore, it is necessary to investigate the aggregation behavior of residual polymer in water. Currently, a large number of reports are focused on the effect of temperature and concentration of salt on the aggregation behavior in water of the polymer used in polymer flooding (Han et al. 2012; Zhao et al. 2009; Liu et al. 2016; Zhong et al. 2010). However, no report has been found which discusses the effect of emulsified oil, suspended solids, Fe3+, Fe2+, cationic water clarifier and SR bacteria, on the aggregation behavior of the residual polymer during the treatment process of produced water. Generally, dynamic light scattering (DLS) and fluorescent microscopy methods (Liu et al. 2016; Zhong et al. 2010) are most frequently used to study the aggregation behavior of polymers in water. Hence, these two methods were adopted in this paper to systematically investigate the effects of emulsified oil, suspended solids, Fe3+, Fe2+, cationic water clarifier and SR bacteria on the aggregation behavior of residual polymer. The results should be helpful for analyzing the stability of residual HMPAM in TOWPF.
2 Experiments
2.1 Materials and instruments
Oily wastewater treatment process in one offshore oil field in China
Water quality of TOWPF in buffer vessel in Fig. 1
| HMPAM concentration, mg/L | Oil content, mg/L | Suspended solid content, mg/L | Fe3+ + Fe2+ concentration, mg/L | Cationic water clarifier concentration, mg/L | SR bacteria, ind/mL |
|---|---|---|---|---|---|
| 60 | 30 | 15 | 0.4 | 40 | 110 |
Cationic water clarifier used was provided by the CNOOC EnerTech-Drilling and Production Co. (Tianjin, China). Pyrene was obtained from Aladdin-Reagent Corporation (Shanghai, China).
The fluorescence spectrum was measured with a LS55 fluorescence spectrophotometer (PerkinElmer Corporation, UK).
Dynamic light scattering (DLS) experiments were performed using Brookhaven Instruments 90Plus/BI-MAS (Brookhaven Instruments, NY, USA). Hydrodynamic radius (R h) was obtained from the DLS results and calculation according to the CONTIN algorithm.
Size exclusion chromatography (SEC) analysis was conducted at 30 °C using a Waters 515 liquid chromatograph connected with a Waters 2410 refractive index detector. The gel permeation column was linear ultrahydrogel (7.8 × 300 mm2), and the solvent used was distilled water. Polymer standards of dextran were used according to National Institute for the Control of Pharmaceutical and Biological Products (NICPBP, China). The polymer samples were dissolved in 0.1 M NaCl solution and analyzed at a flow rate of 0.8 mL min−1. The number average molecular weight (M n), weight average molecular weight (M w) and polydispersity index (PDI) of the polymer samples were measured by SEC.
2.2 Extraction of residual HMPAM in TOWPF
Molecular structure of HMPAM
2.3 Aggregation behavior of residual HMPAM
2.3.1 Preparation of residual HMPAM solution containing pyrene
Composition of simulation formation, mg/L
| NaCl | KCl | CaCl2 | MgCl2·6H2O | Na2SO4 | Na2CO3 | NaHCO3 |
|---|---|---|---|---|---|---|
| 7341 | 66 | 764.7 | 1327 | 126 | 25 | 429 |
2.3.2 Mixture of residual HMPAM solution containing pyrene with different substances
Firstly, the substances which are listed in Table 1, such as oil, suspended solids and Fe3+, were added, respectively, to 800 mL HMPAM solution containing pyrene (the dosage of substance is given in Table 1).
Picture of tubulated bottle
2.3.3 Fluorescence spectrum and DLS
Firstly, four tubulated bottles were kept at 65 °C for 0, 8, 24 and 48 h, respectively. Then, different samples were obtained successively from the bottom of the tubulated bottle. The first 50 mL was the bottom solution, the intermediate 100 mL was the middle solution, and the last 50 mL was the top solution.
The solutions at different layers were filtered by 0.8-μm microporous membrane, and then, the aggregation behavior of residual HMPAM was investigated by using the fluorescence spectrum and DLS result.
Because hydrophobic groups in HMPAM were not water-soluble, they would aggregate and hydrophobic domains can be formed by hydrophobic groups from one HMPAM molecule or several HMPAM molecules (Zhang et al. 2015a, b; Fang et al. 2014). Pyrene would be soluble in the hydrophobic domain. The vibronic structure of the fluorescence spectrum of the monomeric pyrene is known to be sensitive to the local polarity. In particular, the I 1/I 3 ratio of the intensities of the first and third vibronic peaks increases on going from aliphatic to polar solvents (Aguiar et al. 2003; Kim et al. 2000; Ismail 2008) and can be used as an index of the effective local polarity of the pyrene solubilization site in the hydrophobic domain. The ratio I 1/I 3 is the ratio of the intensity of peak I 1 (374.0 nm) to that of peak I 3 (385.0 nm) of the vibration fine structure of pyrene monomer emission. In addition, usually, the I 1 or I 3 would increase with the number of hydrophobic domains because more pyrene can be soluble in the solution when there were more hydrophobic domains. Therefore, the value of I 1 can reflect the number of hydrophobic domains at the same experimental condition, whereas the R h obtained by DLS can reflect the size of HMPAM aggregates.
3 Results and discussion
3.1 Characterization of residual HMPAM
Characterizations of residual HMPAM
| M n, g/mol | M w, g/mol | M η , g/mol | PDI |
|---|---|---|---|
| 3.61 × 105 | 1.41 × 106 | 1.00 × 106 | 3.91 |
As shown in Table 3, the molecular weight of residual HMPAM was not high, but its polydispersity was high. Due to the low molecular weight and its amphiphilic property, its mobility may be similar to that of small molecular weight surfactants. There was intermolecular aggregation for residual HMPAM.
3.2 Fluorescence spectrums
Fluorescence spectra of blank residual HMPAM solution at different layers and different times
I 1/I 3 of blank residual HMPAM solution at different layers and I 1,t /I 1,0h at different times
| Layer | I 1/I 3 | Time, h | I 1,t /I 1,0h | ||
|---|---|---|---|---|---|
| 8 h | 24 h | 48 h | |||
| Top layer | 0.84 | 0.83 | 0.84 | 8 | 1.06 |
| Middle layer | 0.85 | 0.84 | 0.88 | 24 | 1.38 |
| Bottom layer | 0.85 | 0.83 | 0.83 | 48 | 1.52 |
Influence of different factors on the fluorescence spectra of residual HMPAM solution at different layers and different times
| Layer | I 1/I 3 | Time, h | I 1,t /I 1,0h | ||
|---|---|---|---|---|---|
| 8 h | 24 h | 48 h | |||
| The influence of oil | |||||
| Top layer | 1.03 | 1.02 | 1.01 | 8 | 1.15 |
| Middle layer | 1.01 | 1.01 | 1.01 | 24 | 1.19 |
| Bottom layer | 1.04 | 1.01 | 1.01 | 48 | 1.22 |
| The influence of suspended solids | |||||
| Top layer | 0.97 | 0.96 | 0.95 | 8 | 1.13 |
| Middle layer | 0.96 | 0.96 | 0.95 | 24 | 1.37 |
| Bottom layer | 0.97 | 0.96 | 0.95 | 48 | 1.62 |
| The influence of Fe3+ | |||||
| Top layer | 1.17 | 1.17 | 1.18 | 8 | 1.07 |
| Middle layer | 1.15 | 1.18 | 1.17 | 24 | 1.13 |
| Bottom layer | 1.17 | 1.17 | 1.18 | 48 | 1.55 |
| The influence of Fe2+ | |||||
| Top layer | 1.17 | 1.18 | 1.20 | 8 | 1 |
| Middle layer | 1.17 | 1.19 | 1.18 | 24 | 1.40 |
| Bottom layer | 1.17 | 1.19 | 1.17 | 48 | 1.89 |
| The influence of cationic water clarifier | |||||
| Top layer | 1.16 | 1.18 | 1.18 | 8 | 1 |
| Middle layer | 1.16 | 1.18 | 1.20 | 24 | 1.06 |
| Bottom layer | 1.16 | 1.18 | 1.20 | 48 | 1.14 |
| The influence of SR bacteria | |||||
| Top layer | 1.19 | 1.19 | 1.20 | 8 | 1.24 |
| Middle layer | 1.19 | 1.20 | 1.18 | 24 | 1.43 |
| Bottom layer | 1.19 | 1.20 | 1.19 | 48 | 1.50 |
Change in aggregation behavior of residual HMPAM after addition of different substances (taking Fe2+ and cationic water clarifier as example)
Table 5 also showed that after addition of different substances, the I 1,t /I 1,0h increased with time. Compared to the I 1,48h/I 1,0h of blank HMPAM solution, after addition of oil and cationic water clarifier, the I 1,48h/I 1,0h data were much smaller. This result suggested that oil and cationic water clarifier could inhibit the increase in the hydrophobic domains. After addition of Fe3+ and SR bacteria, HMPAM solution had similar I 1,48h/I 1,0h as the blank ones, indicating that Fe3+ and SR bacteria almost had no influence on the increase in hydrophobic domains. However, after addition of Fe2+ and suspended solids, the HMPAM solution had much larger I 1,48h/I 1,0h than blank ones, indicating that Fe2+ and suspended solids were favorable to the increase in hydrophobic domains. Usually, increasing the hydrophobic domains means an increasing degree of aggregation. In summary, with Fe2+, HMPAM solution had the largest aggregation degree (I 1,48h/I 1,0h = 1.89); with cationic water clarifier, HMPAM solution had the smallest aggregation degree (I 1,48h/I 1,0h = 1.14). After addition of Fe2+, the chelation between Fe2+ and the carboxyl groups in HMPAM would increase with time over 48 h. Therefore, the number of hydrophobic domains increased significantly with time. Cationic water clarifier had much larger molecular weight and positive charge than Fe2+, and the electrostatic charge neutralization between cationic water clarifier and HMPAM was strong and fast. Addition of cationic water clarifier would result in larger HMPAM aggregates forming quickly. The number of hydrophobic domains would not increase with time significantly over 48 h.
3.3 DLS results
Effects of Fe2+ and cationic water clarifier on the relationship between R h of HMPAM and time
In addition, when Fe2+ was added in solution, the R h of it was similar to that of blank sample. But when t cationic water clarifier was added in solution, the R h of it was much larger than that of blank ones. The results also confirmed the aggregation behavior of residual HMPAM shown in Fig. 5.
4 Conclusion
In this research, the influences of emulsified oil, suspended solids, Fe3+, Fe2+, cationic water clarifier and SR bacteria on the aggregation behavior of residual HMPAM in TOWPF were studied by fluorescence spectroscopy and DLS. After the addition of these substances into residual HMPAM solution, the I 1/I 3 was much larger than that of blank and not influenced by time. Oil and cationic water clarifier could inhibit the increase in hydrophobic domains. Fe2+ and suspended solids were helpful for the increase in hydrophobic domains. Fe3+ and SR bacteria had no great influence on the increase in hydrophobic domains. In summary, when there was Fe2+, HMPAM solution had the largest aggregation degree by the increasing number of HMPAM aggregates. When there was cationic water clarifier, HMPAM solution had the smallest aggregation degree because of its strong electrostatic charge neutralization with HMPAM.
Notes
Acknowledgements
We acknowledge the supply of SR bacteria by Dr. Guihong Lan, who works in the School of Chemistry and Chemical Engineering, Southwest Petroleum University, in China. This work was supported by the Scientific Research Project of CNOOC (China) (Grant No. CNOOC-KJ 125 ZDXM 06 LTD NFGC 2014-01).
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