Chemical Engineering Program, COPPE, Federal University of Rio de Janeiro, P.O. Box 68502, Rio de Janeiro, RJ, 21945-970, Brazil.
Petrobras, Cenpes, Av. Horacio Macedo 950, Rio de Janeiro, RJ, 21941-915, Brazil.
Environ Sci Pollut Res Int. 2016 Nov;23(22):22947-22956. doi: 10.1007/s11356-016-7476-5. Epub 2016 Aug 30.
This paper comes out from the need to provide an improvement in the current oil refinery wastewater treatment plant (WWTP) aiming to generate water for reuse. The wastewater was pretreated and collected in the WWTP after the biological treatment unit (bio-disks) followed by sand filtration. Ozonation (ozone concentration from 3.0-60 mgO L), UV (power lamp from 15 to 95 W), HO (carbon:HO molar ratio of 1:1, 1:2, and 1:4), and two advanced oxidation processes (UV/O and UV/HO) were investigated aiming to reduce the wastewater organic matter and generate water with suitable characteristics for the reverse osmosis operation and subsequent industrial reuse. Even after the biological and filtration treatments, the oil refinery wastewater still presented an appreciable amount of recalcitrant organic matter (TOC of 12-19 mgC L) and silt density index (SDI) higher than 4, which is considered high for subsequent reverse osmosis due to membrane fouling risks. Experiments using non combined processes (O, HO, and UV only) showed a low degree of mineralization after 60 min of reaction, although the pretreatment with ozone had promoted the oxidation of aromatic compounds originally found in the real matrix, which suggests the formation of recalcitrant compounds. When the combined processes were applied, a considerable increase in the TOC removal was observed (max of 95 % for UV/O process, 55 W, 60 mgO L), likely due the presence of higher amounts of reactive species, specially hydroxyl radicals, confirming the important role of these species on the photochemical degradation of the wastewater compounds. A zero-order kinetic model was fitted to the experimental data and the rate constant values (k, mgC L h) ranged from 4.8 < k < 11 ([O] = 30-60 mg L), and 8.6 < k < 11 (C:HO from 1:1 to 1:4). The minimum and maximum electrical energy per order (E ) required for 60 min of treatment were calculated as 5.4 and 81 Wh L, respectively, for UV/O (15 W, 60 mgO L) and UV/HO (95 W, 1C:1HO). Good results in terms of water conditioning for reverse osmosis operation were obtained using UV/HO process with initial molar ratio of 1 C:2 HO (UV lamp 55 W) and 1 C:4 HO (UV lamp 95 W), and total organic carbon (TOC) removals of 62 % (SDI = 1.8) and 74 % (SDI = 2.0) were achieved, respectively, after 60 min. The treated wastewater followed to the reverse osmosis system, which operated with an adequate flux of permeate, was very efficient to remove salt and generate a permeate water with the required quality for industrial reuse.
本文源自于改进当前炼油厂废水处理厂(WWTP)以生成可再利用水的需求。废水在生物处理单元(生物转盘)后经过预处理并在 WWTP 中收集,然后进行砂滤。臭氧处理(臭氧浓度为 3.0-60 mgO L)、紫外线(功率灯为 15-95 W)、HO(碳:HO 摩尔比为 1:1、1:2 和 1:4)和两种高级氧化工艺(UV/O 和 UV/HO)被研究,目的是减少废水中的有机物并生成具有适合反渗透操作和后续工业再利用的特性的水。即使经过生物和过滤处理,炼油厂废水仍含有相当数量的难处理有机物(TOC 为 12-19 mgC L)和浊度密度指数(SDI)高于 4,这对于随后的反渗透来说是高风险的,因为存在膜污染的风险。使用非组合工艺(仅 O、HO 和 UV)的实验表明,在 60 分钟的反应后,矿化程度较低,尽管臭氧预处理促进了原本存在于实际基质中的芳香族化合物的氧化,这表明形成了难处理的化合物。当应用组合工艺时,TOC 的去除率显著增加(UV/O 工艺最高可达 95%,55 W,60 mgO L),可能是由于存在更多的反应性物质,特别是羟基自由基,这证实了这些物质在废水化合物的光化学降解中的重要作用。实验数据拟合了零级动力学模型,得到的速率常数(k,mgC L h)值范围为 4.8<k<11([O]为 30-60 mg L)和 8.6<k<11(C:HO 为 1:1 至 1:4)。对于 UV/O(15 W,60 mgO L)和 UV/HO(95 W,1C:1HO),计算了 60 分钟处理所需的每阶最小和最大电能(E)分别为 5.4 和 81 Wh L。使用初始摩尔比为 1 C:2 HO(UV 灯 55 W)和 1 C:4 HO(UV 灯 95 W)的 UV/HO 工艺,得到了良好的反渗透运行水调节效果,TOC 去除率分别为 62%(SDI=1.8)和 74%(SDI=2.0),在 60 分钟后达到。处理后的废水随后进入反渗透系统,反渗透系统的渗透通量充足,能够有效地去除盐分,并生成符合工业再利用要求的渗透水。