Treatment of oil refinery wastewater containing spent caustic soda using electrocoagulation method

Document Type : Original Research

Authors
1 MSc Student in Civil-Environmental Engineering, Kharazmi University
2 1. Kharazmi University, Faculty of Engineering, Civil Engineering Department
3 Assistant professor and head of water and wastewater treatment and reuse, Research Institute of Petroleum Industry
4 Assistant professor, Research Institute of Petroleum Industry
Abstract
A vital stage in oil refining is elimination of hydrogen sulfide, which is done by means of sodium hydroxide solution in petrochemical industries, leaving a spent caustic soda (NaOH solution) as the product. In the process, hazardous gases react with sodium hydroxide and hydrogen sulfide solutions and Thiol compounds to form a rich brown to nearly black effluent demonstrating the fragrant toxic components such as methanethiol, enzene, toluene and phenol. Despite all these odorous noxious organosulfur compounds, spent caustic soda leads to environmental problems due to its alkalinity (pH>12), salinity (5-12 wt.%) and high sulfide content (1-4 wt.%). Spent NaOH was registered as industrial dangerous waste in resource conservation and recovery act law. Inefficient and inappropriate management in spent NaOH treatment and disposal causes stability challenges, reduction in energy resources and water security attenuation. Techniques for spent caustics treatment have been neutralization with acid, wet air oxidation, combination of neutralization and Fenton (i.e. electro-Fenton), biologic treatment and ignition each of which would face some limitations. In recent decades, electrocoagulation (EC) has engrossed much attention as an Environmental-friendly and effective process. In addition, the EC process is a potential suitable way for treatment of wastewater with a view to costs and environment. Furthermore, EC offers further advantages as simple operation facilities, small occupying area, dispensability of chemical additives and short treatment time. EC often consists of anodes and DC cathodes a part of which are immersed in wastewater container. Shape, number and configuration of electrodes may be different but rectangular types are preferred. The widespread anodes are iron and aluminum based for their availability, reasonable cost and harmless media. In electrocoagulation, electrolysis takes place to dissolve metal anode (sacrificial electrode) in wastewater. Metal ion flow from sacrificial electrode as coagulant surrounds wastewater particles. After release of Al3+ and Fe2+, the ions react with hydroxide groups and metal hydroxides turn to insoluble agglomerates able to trap contaminants and increase particle size by complexation of electrostatic attraction. In addition, hydrogen gas produced in cathode, allows agglomerates to float on surface. The object of this study is electrochemical evaluation of COD removal from refinery wastewater, specifically refinery spent caustic, using iron and aluminium (anode) and graphite (cathode) electrodes. Therefore, the effect of key variables including electrode arrangement (bipolar-serie, monopolar-serie and monopolar-parallel), anode electrode material (iron and aluminium), using pierced anode electrode and cathode graphitem initial pH (7-11), electrolysis time (0 to 120 minute), current density (15.6 to 28.125 mA/cm2) was evaluated. The three parameters of current density, electrolysis time and initial pH has been modeled with design expert software with response surface method (RSM) and central composite design (CCD). Impact of other variables has been investigated with single parameter method. According to the results, the optimum conditions including, parallel mono-polar electrode arrangement, aluminium electrode has been achieved. In designing experiments in accordance with the model provided by the software, quadratic analysis design with R2=0.96 had a high accuracy in designing the experiment. According to the model analysis and laboratory work, optimum electrolysis time was 116 min, current density was 25 mA/cm2 and initial pH=8 reached COD removal percentage of 85.1% in vitro and 88.9% for model.

Keywords

Subjects


1. Sahu, O., et al., Treatment of wastewater from sugarcane process industry by electrochemical and chemical process: Aluminum (metal and salt). Journal of Water Process Engineering, 2017. 17: p. 50-62.
2. Fox, C., et al., A preliminary spatial assessment of risk: Marine birds and chronic oil pollution on Canada's Pacific coast. Science of The Total Environment, 2016. 573: p. 799-809.
3. Chen, L., et al., A study on the fabrication of porous PVDF membranes by in-situ elimination and their applications in separating oil/water mixtures and nano-emulsions. Journal of Membrane Science, 2016. 520: p. 760-768.
4. Hu, H., et al., Optimization and Exergy Analysis of Natural Gas Liquid Recovery Processes for the Maximization of Plant Profits. Chemical Engineering & Technology, 2018. 42: p. 182-195.
5. Alipour, Z. and A. Azari, COD removal from industrial spent caustic wastewater: A review. Journal of Environmental Chemical Engineering, 2020. 8(3): p. 103678.
6. Ntagia, E., et al., Electrochemical treatment of industrial sulfidic spent caustic streams for sulfide removal and caustic recovery. Journal of Hazardous Materials, 2020. 388: p. 121770.
7. Delnavaz, M., B. Ayati, and H. Ganjidoust, Prediction of moving bed biofilm reactor (MBBR) performance for the treatment of aniline using artificial neural networks (ANN). Journal of Hazardous Materials, 2010. 179(1): p. 769-775.
8. Reed, B.E., et al., Treatment of Oily Wastes Using High-Shear Rotary Ultrafiltration. Journal of Environmental Engineering, 1997. 123(12): p. 1234-1242.
9. Cumming, I.W., R.G. Holdich, and I.D. Smith, The rejection of oil using an asymmetric metal microfilter to separate an oil in water dispersion. Water Research, 1999. 33(17): p. 3587-3594.
10. Al-Shamrani, A.A., A. James, and H. Xiao, Destabilisation of oil–water emulsions and separation by dissolved air flotation. Water Research, 2002. 36(6): p. 1503-1512.
11. Scholz, W. and W. Fuchs, Treatment of oil contaminated wastewater in a membrane bioreactor. Water Research, 2000. 34(14): p. 3621-3629.
12. Ho, C.C. and C.Y. Chan, The application of lead dioxide-coated titanium anode in the electroflotation of palm oil mill effluent. Water Research, 1986. 20(12): p. 1523-1527.
13. Lai, C.L. and S.H. Lin, Treatment of chemical mechanical polishing wastewater by electrocoagulation: system performances and sludge settling characteristics. Chemosphere, 2004. 54(3): p. 235-242.
14. Yang, C.-L., Electrochemical coagulation for oily water demulsification. Separation and Purification Technology, 2007. 54(3): p. 388-395.
15. Xu, X. and X. Zhu, Treatment of refectory oily wastewater by electro-coagulation process. Chemosphere, 2004. 56(10): p. 889-894.
16. Pikaar, I., et al., Electrochemical Abatement of Hydrogen Sulfide from Waste Streams. Critical Reviews in Environmental Science and Technology, 2015. 45: p. 1555-1578.
17. Harinarayanan Nampoothiri, M.G., A.M. Manilal, and P.A. Soloman, Control of Electrocoagulation Batch Reactor for Oil removal from Automobile Garage Wastewater. Procedia Technology, 2016. 24: p. 603-610.
18. Merma, A.G., et al., Treatment of oily wastewater from mining industry using electrocoagulation: Fundamentals and process optimization. Journal of Materials Research and Technology, 2020. 9(6): p. 15164-15176.
19. SMWW, 5220 CHEMICAL OXYGEN DEMAND (COD) (2017), in Standard Methods For the Examination of Water and Wastewater. 2017.
20. Delnavaz, M. and D. Bahrami, Application of electrochemical coagulation process with iron and aluminum modified by zinc oxide nanoparticles by cyclic voltammetry in removal of reactive blue 19 dye. Sharif Journal of Civil Engineering, 2021.
21. Ben Hariz, I., et al., Treatment of petroleum refinery sulfidic spent caustic wastes by electrocoagulation. Separation and Purification Technology, 2013. 107: p. 150-157.
22. Adhoum, N. and L. Monser, Decolourization and removal of phenolic compounds from olive mill wastewater by electrocoagulation. Chemical Engineering and Processing: Process Intensification, 2004. 43(10): p. 1281-1287.
23. Fekete, É., et al., Electrochemical dissolution of aluminium in electrocoagulation experiments. Journal of Solid State Electrochemistry, 2016. 20: p. 3107–3114.