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Ribeiro 1, Mrcia Dezzoti2 Ana Cludia Cerqueira3, Geraldo Lippel4

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 17-20, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Bi ofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Water is one of the most important natural resources and their proper management is a key component in environmental policies. This is because, although abundant, only 2.5% of the planet's water is fresh water, mostly located in areas of difficult access. This work investigates the process O3/UV coupled with reverse osmosis membranes (RO) in order to meet the standards of the wastewater reuse. The wastewater comes from a biodisc unit located in Gabriel Passos refinery (REGAP, Petrobras). Assays were performed in a photochemical reactor with a volume of 2 L, cooling jacket and internal quartz tube, which were used germicidal UV-C lamps in powers of 15, 55 and 95 W. The range of concentration of ozone employed in the work is 3-10 mg / L for the gas phase and gas flow rate used of 1 L / min. The O3/UV process achieved low removals of TOC, a consequence of the recalcitrant nature of organic matter present in the wastewater. The addition of H2O2 (C: H2O2 = 1:2) was able to achieve 80% removal of TOC. The treated wastewater was led the RO stage which showed high salt removal efficiency, adjusting the wastewater to the more demanding reuse standards. O3/H2O2/UV The process proved effective as a pretreatment step for RO, avoiding the sharp drop in permeate flux.

1. Introduction
The availability of water in the world exceeds by far the human demand. However, the way in which this resource is distributed is a serious problem. This is because, although abundant, only 3% of the planet's water is fresh water, more suitable condition for human consumption, the rest is basically constituted by water in the oceans. And of these 3%, only 0,5% of this water is available in easily accessible locations such as aquifers, lakes and rivers. With regard to water availability, Brazil can be considered a privileged country, having close to 13% of all fresh waters reserve on the planet (Mierzwa, 2005). However, these water resources are unevenly distributed geographically, as the Amazon region accounts for over 80% of water reserves, while the state of Amazonas contains 7.5% of the population (Mancuso, 2003). Besides, the limited availability of water for consumption, the increasing pollution of water bodies, through domestic and industrial wastewaters, aggravates this issue, impacting the drinking water supply in urban centers. The water reuse is defined as the use of water previously used one or more times for any human activity, to meet the needs of other beneficial uses, including the original. The practice of reuse, therefore, leads to many benefits for the industry, both in terms of environmental, economic and corporate image, since the concept of reuse is directly aligned with todays environmental management policy. With regard to the environment, reuse of water contributes to the preservation of water resources, causing thus an increase in water availability for the population by reducing the uptake of water from springs. The economic benefits, in turn, are linked to environmental, as the company shall not

______________________________ 1 Master, Chemical Engineer - PEQ/COPPE Federal University of Rio de Janeiro 2 Doctor, Chemical Engineer - PEQ/COPPE Federal University of Rio de Janeiro 3 Doctor, Chemical Engineer - PETROBRAS 4 Doctor, Chemical Engineer - PEQ/COPPE Federal University of Rio de Janeiro

Rio Oil & Gas Expo and Conference 2012 add to their product costs related to charging for water use. Therefore, the reuse of water is an alternative capable of improving the efficiency of water management, providing the decrease of water consumption and the minimization of waste generated. In this sense, the oxidative processes and membrane separation techniques are employed when the reuse of the wastewater is taken as objective. The advanced oxidation processes (AOP) are promising technologies for the treatment of complex wastewaters, such as refineries and industrial wastewaters, being employed in order to remove these difficult degradation organic pollutants. The POA differs from conventional oxidation processes for the generation of hydroxyl radicals, which are radical species with high oxidizing power, acting to convert the contaminants into less toxic products, breaking the chain of polluting by-products generating less complex than can be biologically treated or under optimal conditions, mineralize most organic pollutants by converting them to carbon dioxide (CO2), water and inorganic ions. The hydroxyl radicals are radicals having high oxidizing power, much larger than the more commonly used oxidants such as chlorine. Moreover, the POAs ability of mineralizing various pollutants is favored by these non-selective hydroxyl radicals, which allows the radicals reaction with a variety of organic compounds. The hydroxyl radical also stands for the kinetic reaction with pollutants, having extremely high values for most organic compounds. The reverse osmosis is a membrane separation process often used to retain low molecular weight solutes, the order of angstroms, such as inorganic salts. It has the advantage of being a quite developed process for treating wastewater, retaining microorganisms and anthropogenic organic compounds, being compact systems, and can achieve more than 90% removal of dissolved solids. A major problem encountered in the operation of reverse osmosis membranes is the control of fouling. These inlays are undesirable phenomena in which the flux is reduced to alarming levels, which may cripple the operating costs of the process.

2. Materials and Methods

The industrial wastewater used was received from the Gabriel Passos Refinery (REGAP) - Petrobras, located in Betim. The wastewater was collected after sand filters located after the biodisc unit. The parameters used in the characterization were pH, conductivity, turbidity, chemical oxygen demand (COD), total organic carbon (TOC), absorbance at the wavelength of 254 nm (ABS254), ammonia (NH4+) and total suspended solids (TSS) Table 2.1 illustrates the range values of these parameters. Table 2.1 - Characterization of the industrial wastewater used in the study pH 6,73-7,61 Conductivity (S/cm) 1127-1953 Turbidity (NTU) 0,02-0,26 COD (mg/L) 39-81 TOC (mg/L) 12,2-16,6 ABS254 0,33-0,39 NH4+ (mg/L) 1-17 Total Solids (mg/L) 7-57

The POA and ozonation assays were performed in a bench scale photochemical reactor, with a volume of 2.5 L and inner tube of quartz, in which germicidal UV-C lamps were connected in the powers of 15, 55 and 95 W. The ozone concentrations used were 3-10 O3 mg/L in the gas phase. The gas flow used (1 L/min) and wastewater volume (2 L) added to the reactor were the same for all tests. The reaction time was 60 minutes for all experiments and aliquots were withdrawn every 10 minutes to monitor the organic matter removal. After the advanced oxidation treatment the wastewater was sent to the reverse osmosiss stage to reduce the salt concentration of the wastewater, allowing its reuse in cooling towers or for steam generation in high pressures boilers, for example. Figure 2.1 illustrates the photochemical reactor used, as well as the reverse osmosis unit.

Figure 2.1 Photochemical reactor and the bench scale reverse osmosis unit 2

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3. Results and Discussion

3.1 Ozonation In a primary analysis, ozonation were performed on O3 concentrations of 3, 6 and 10 mg/L. Table 3.1 summarizes the results obtained after 60 minutes of reaction. Table 3.1 - Results of ozonation of the wastewater after 60 minutes of reaction Removals (%) TOC ABS254 SUVA 3 mg O3/L 5 53 53 6 mg O3/L 8 67 64 10 mg O3/L 9 66 62

Under the conditions employed in the study, the ozonation process did not achieved good efficiency in removing TOC, presenting lower removal values. These results are in agreement with the literature, since ozonation rarely leads to complete mineralization of compounds. Probably one of the causes of low TOC removal occurs because ozone in the pH used, does not generate hydroxyl radicals in appreciable quantity. The O 3 decompose into hydroxyl radicals in basic pH of above 10 (Dezotti, 2008; Lucas et al., 2010). At neutral pH, about 7, about 50% of the dissolved ozone decomposes in that OH radicals. Thus, the predominant mechanism of degradation under the conditions employed in this study is the direct reaction with molecular ozone, which due to its selectivity does not lead to mineralization of pollutants. The reductions and SUVA and ABS254, however, were above 60%, indicating a change in characteristics of the wastewater, making it more biodegradable (Gong et al., 2008; Gottshalk et al., 2010). 3.2 Advanced Oxidation Processes - O3/UV and O3/H2O2/UV Coupling of the ozonation process with the ultraviolet (O 3/UV) was used in the work leading to further generation of hydroxyl radicals which would enable a greater removal of the organic matter in the wastewater. The pH and conductivity of the wastewater remained constant for all experiments. Table 3.2 condenses the removal values of the analyzed parameters for the tests at concentrations of 3, 6 and 10 mg/L. Table 3.2 - Removals of color, TOC, SUVA and ABS254 for the O3/UV process at different operating conditions after 60 min irradiation Removal Efficiency (%) [O3] (mg/L) 3 3 3 6 6 6 10 10 10 UV-C Lamp Power (W) 15 55 95 15 55 95 15 55 95 Color 78,0 9,0 79,9 13,5 90,0 2,0 89,0 1,4 93,1 2,0 94,5 4,0 90,0 1,0 91,7 0,6 93,4 1,5 TOC 3,6 0,6 11,5 0,3 10,9 0,8 13,4 0,4 18,4 2,7 21,4 2,9 10,6 0,5 16,5 2,1 17,3 2,1 ABS254 56,3 1,2 68,1 4,2 64,1 3,2 74,7 6,6 84,0 2,7 83,6 1,5 75,6 0,3 84,5 0,1 81,4 2,1 SUVA 56,0 3,0 64,0 4,6 60,1 4,6 70,8 7,5 80,7 2,2 79,1 1,1 73,6 0,3 81,9 0,1 77,7 0,7

Low removals were obtained using a concentration of 3 mg/L of ozone, for all UV-C lamps, which are similar to the removals achieved by the ozonation process, without the addition of ultraviolet light. This indicates that the addition of ultraviolet light (even at higher powers) was not capable of decomposing ozone in hydroxyl radical, possibly due to low concentration of O3 dissolved in the aqueous matrix. Considering the wastewaters pH, around neutrality, one can assume that the mechanism of degradation of organic matter was again dominated by direct attack of molecular ozone. For the operation condition of 6 mg/L, the O3/UV process achieved low TOC removal again, with a maximum removal of 21% on average, for the lamp of 95 W. Were obtained good removals of color, SUVA and 3

Rio Oil & Gas Expo and Conference 2012 ABS254, about 90 to 80% for the first and the last two. Proper removal of ABS254 suggests that, although mineralization and removal the recalcitrant organic matter cannot be achieved, the O3/UV process can change the wastewaters nature, acting to generate less complex byproducts which can then be biologically degraded (Gong et al., 2008). By employing a higher O3 concentration (10 mg/L) were again obtained low TOC removal (17% on average, to the 95 W lamp). The removal of color, SUVA and ABS254 again showed removals over 90% for the first and 75% for the last two. The values of low TOC removal shows the recalcitrant compounds present in the aqueous matrix, which the O3/UV process, in the conditions employed in the study, failed to remove. Increasing the concentration of O3, under the conditions used in this study, had a positive impact in the TOC removal, due to the higher concentration of ozone dissolved in the aqueous matrix. This increase in TOC removal is due to the decomposition of the O3 in hydroxyl radicals, favored by the use of ultraviolet radiation. The radical mechanism presents relevance in the ozone concentrations of 6 and 10 mg/L, while in the concentration of 3 mg/L the predominant mechanism is the reaction via molecular ozone, as mentioned above. The O3 concentration of 10 mg/L showed the same TOC removal that the concentration of 6 mg/L, possibly due to mass transfer limitations of the reactor, preventing further dissolution of the O3 in the aqueous matrix. The increase in UV light intensity has positivey impacted the removal of organic matter and, consequently, the efficiency of the O3/UV process, as can be observed by the removal of TOC. The use of the 95 W lamp did not improved the efficiency of the process, achieving the same TOC removal values of the 55 W lamp. This fact may suggest that, under the experimental conditions used, may be occurring an excess of photons, since low concentrations of ozone are employed in the study. After the completion of all O3/UV tests, the best operating condition was selected based on TOC removal. Analyzing the results can be inferred that the greatest reductions are obtained in the TOC concentration of 6 mg/L. Concomitantly, it was observed that the use of the 95 W lamp did not caused significant improvement in the TOC removal when compared with the 55 W lamp. Therefore, the experimental condition of 6 mg/L of O3 with the lamp of 55 W was the chosen experimental conditions for the subsequent stages. However, as evidenced, even the better O3/UV process condition provides low TOC removal. Therefore, in order to improve the removal of organic matter and thus reduce potential fouling on the reverse osmosis membrane, additional tests were carried out employing a reaction time of 180 minutes for the O3/UV process, besides the addition of hydrogen peroxide in the C:H2O2 proportions of 1:1 and 1:2. Table 3.3 summarizes the results obtained from the best operating condition observed in the O3/UV stage. Table 3.3 - Additional tests ([O3] = 6 mg/L and 55 W UV-C lamp power) Removal Efficiency (%) Process O3/UV O3/H2O2/UV O3/H2O2/UV O3/UV O3/H2O2/UV O3/H2O2/UV C:H2O2 Proportion 1:1 1:2 1:1 1:2 Reaction time (min) 60 60 60 180 180 180 TOC 18 3 42 1 67 1 50 1 68 1 80 2 ABS254 84 3 90 1 92 1 90 1 92 1 93 1

The addition of the H2O2 on the O3/UV process caused a great impact on the TOC removal, both for the C:H2O2 proportion of 1:1 as for the 1:2. In the C:H2O2 1:1 proportion, the addition of H2O2 caused a 133% increase in TOC removal, while adding a greater amount of H2O2 (C:H2O2 proportion of 1:2) resulted in an increase of 272% in TOC removal. This fact was expected, since the photolysis of H2O2 generates more hydroxyl radicals to the system, increasing its power and contributing to the oxidative removal of organic matter. Moreover, the kinetics of the O3/UV process is greatly favored by the increase of the reaction time, as can be seen in Table 3.3. The use of reaction time of 180 minutes caused an increase of 178% removal of TOC. This increase was already expected. Therefore, the O3/UV reaction with the addition of H2O2 in the C:H2O2 proportion of 1:2 and a reaction time of 180 minutes yielded high removal of organic matter (80% TOC removal and 93% ABS254 removal) and a 515% increase in removal efficiency compared with the O3/UV process performed after 60 minutes of reaction. These results show that the oxidation via radical OH is much more efficient for removing TOC on this wastewater than the reaction via molecular ozone, even if small amounts of hydrogen peroxide were added. The effluent was led to the stage of RO.

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3.3 Reverse Osmosis The Silt Density Index (SDI) assays were conducted for the wastewater treated by advanced oxidation process and the raw wastewater in order to evaluate the decline of the fouling potential of the wastewater for use in the subsequent step of reverse osmosis. The wastewaters SDI15 was 5.9 0.1 (pH = 7.5 and T = 25 C) which characterizes the need for the pre-treatment step before the reverse osmosis stage (Mosset et al., 2008; Dias , 2011). SDI15 analysis of the wastewater treated by the O3/UV and O3/H2O2/UV processes are shown in Table 3.4. Table 3.4 - SDI15 results for the wastewater after the oxidative treatment Process O3/UV O3/H2O2/UV C:H2O2 Proportion 1:2 Reaction Time (min) 180 180 pH 7,7 8,3 T (C) 25 25 SDI15 4,9 0,1 5,3 0,1

The SDI15 results obtained presented values around 5.0, the required range for use in equipments such as reverse osmosis. For the permeation tests of the reverse osmosis stage were analyzed characteristics of the feed, permeate and concentrate, and the permeate flow, with all the permeation tests performed in triplicate. The parameters used for the characterization of the effluent were pH, conductivity, TOC and ammonia. The monitoring of the conductivity and the TOC, respectively, during the test for currents permeate are shown in Figure 3.1.

Figure 3.1 - TOC and conductivity values for the permeate for the permeations tests ( ) P = 30 bar ( ) P = 25 bar. In the permeation test the removal efficiency was 95% for TOC and conductivity, and an ammonia removal of 73% for the 25 bar pressure and 96% conductivity removal and 88% TOC removal with NH4+ removal of 77% for the pressure of 30 bar, values obtained for 25% recovery (R). The permeate flux was relatively constant at around 95 Lh-1m-2. Table 3.5 shows the characteristics of the current feed, permeate and concentrate for testing the operating pressures of 25 and 30 bar. Table 3.5 - Characteristics of the feed, permeate and concentrate to the reverse osmosis test at pressures of 25 and 30 bar and R = 25% and with effluent ps-O3/H2O2/UV irradiation for 180 minutes Pressure (bar) 25 Feed Permeate (R = 25%) Concentrate (R = 25%) Feed Permeate (R = 25%) Concentrate (R = 25%) pH 7,2 0,5 6,0 0,7 7,6 0,1 7,5 0,1 7,9 0,1 7,7 0,1 (S/cm) 1314 152 58 23 1707 1 1184 15 42 8 1643 103 TOC (mg/L) 4,1 0,3 0,2 0,1 3,3 1,0 4,0 0,3 0,5 0,3 4,2 0,4 NH4+ (mg/L) 1,04 0,09 0,26 0,01 0,49 0,02 0,52 0,17 0,12 0,05 0,37 0,09


Rio Oil & Gas Expo and Conference 2012 After the reverse osmosis step, the characteristics of the effluent were tested for their ability to meet the required standards for industrial reuse. It was inferred that the reverse osmosis step provided wastewater suitable for the most demanding industrial reuse conditions, such as high-pressure boilers, as shown in Table 3.6. Table 3.6 Comparison of the quality parameters of effluent generated by coupling HI-POA and required to re-use in high pressure boilers Parameters pH Conductivity (S/cm) Turbidity (NTU) COD (mg/L) TOC (mg/L) ABS254 Ammonia (mg/L) TSS (mg/L) Raw wastewater 6,73 - 7,61 1127 - 1953 0,02 - 0,26 39 - 81 12,2 - 16,6 0,33 - 0,39 1 - 17 7 57 Wastewater after the AOP step 7,3 - 8,2 1368 - 1463 3,2 - 4,8 0,026 - 0,030 3 - 17 Wastewater after the RO step 7,9 0,1 42 8 0,5 0,3 0,12 0,05 High Pressure Boiler 8,2 - 9,0 60 1 1 0,5

The long-term assays consisted of permeating the wastewater continuously for 150 hours in order to evaluate the tendency of the membrane for biofilm formation, recording the flux from time to time. Long-term tests were conducted for the wastewater treated by the O3/UV O3/H2O2/UV processes, with a 30 bar pressure. The decline of the permeate flux is shown in Figure 3.2.

Figure 3.2 Evaluation of the permeate flux decline in permeation testing long term ( ) and O3/UV ( ) O3/H2O2/UV The process O3/UV, although good removal of organic matter, has not been able to avoid the formation of biofilm on reverse osmosis membrane, showing marked decrease in permeate flow after 150 hours. The process O3/H2O2/UV, however, showed no sharp decline in the permeate flow, which confirms the results of removal of organic matter. Table 3.7 summarizes the values of fall of permeate flow. Table 3.7 - Values of permeate flow permeation after 150 test hours. Process O3/H2O2/UV O3/UV Inicial Flux (L h-1 m-2) 66 92 Final Flux (L h-1 m-2) 52 26 Flux decline (%) 21 71

Was made Epifluorescence microscopy after membranes reverse osmosis tests in order to analyze viable cells, forming biofilm. In these experiments, living cells are stained green and dead cells, red. Was performed epifluorescence microscopy biotratado effluent and effluent pretreated by the process O3/H2O2/UV (Fig. 3.3):

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Figure 3.3 Epifluorescence microscopy analysis of the membranes (a) and (b) biotratado effluent, (c) and (d) postprocess effluent O3/H2O2/UV It can be observed that even the pretreated effluent showed POA for biofilm formation. However, the presence of micro-organisms on the membrane was lower when the effluent is treated by the process O3/H2O2/UV proving the efficiency of the pre-treatment. When comparing Figures 3.3ce 3.3d can observe most of the presence of dead cells that live on the membrane after treatment of the effluent by the oxidative process.

DEZOTTI, M., Processos e Tcnicas para o Controle Ambiental de Efluentes Lquidos. 1 ed. Rio de Janeiro, Epapers Servios Editoriais Ltda, 2008. DIAS, I. N., 2011, MBBR Acoplado a Filtro Lentro de Areia e a Osmose Inversa para o Tratamento de Efluente da Indstria de Petrleo Visando Reuso, Dissertao de Mestrado, COPPE/UFRJ, Rio de Janeiro, RJ, Brasil. GONG, J., LIU, Y., SUN, X., O3 and UV/O3 Oxidation of Organic Constituents of Biotreated Municipal Wastewater, Water Research, n. 42, pp. 1238-1244, 2008. GOTTSCHALK, C., LIBRA, J. A., SAUPE, A., Ozonation of Water and Waste Water A Practical Guide to Understand Ozone and its Applications, 2 ed. WILEY-VCH Verlga GmbH & Co. KGaA, Weinheim, 2010. LUCAS M. S., PERES J. A., PUMA G. L., Treatment of Winery Wastewater by Ozone-based Advanced Oxidation Processes (O3, O3/UV e O3/H2O2/UV) in a Pilot-scale Bubble Column Reactor and Process Economics, Separation and Purification Technology, n. 72, pp. 235-241, 2010. MANCUSO P. C. S. & SANTOS H. F., Reso de gua, 1 Ed. Manole, Barueri, SP, 2003.

Rio Oil & Gas Expo and Conference 2012 MIERZWA, J.C., HESPANHOL, I., gua na indstria - Uso racional e reso., In: Oficina de Textos, So Paulo, 2005 MOSSET, A., BONNELYE, V., PETRY, M. et al., The Sensitivity of SDI Analysis: from RO Feed Water to Raw Water, Desalination, n. 222, pp. 17-23, 2008. SCHON, H. K., VIGNESWARAN, S., KIM, IN S. et al., Fouling of Ultrafiltration Membrane by Effluent Organic Matter: A Detailed Characterization using Different Organic Fractions in Wastewater, Journal of Membrane Science, n. 278, pp. 232-238, 2006.