Chemical dechlorination for the treatment of PCBs present in transformer oil (Sovtol-10): parameter study Margie Zorrilla Velazcoa*, Petra G. Velazco Pedrosoa, Gretel Villanueva Ramosb, Herman Van Langenhovec aStudy Center of Applied Chemistry. bFaculty of Chemistry and Pharmacy. Central University “Marta Abreu” of Las Villas. Road to Camajuani Km. 5 ½, CP 54830, Villa Clara, Cuba. cResearch Group EnVOC, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B9000, Belgium. Descloración química para el tratamiento de PCBs presente en aceite de transformador (Sovtol-10): parámetro de estudio Descloració química per al tractament de PCBs presents en olis de transformador (Sovtol-10): paràmetre d’estudi Recibido: 21 de febrero de 2012; aceptado: 24 de mayo de 2013 RESUMEN tions: PEG 400, KPEG/oil weight ratio of 30 and KOH/PEG mole ratio 2 for 2 hours of reaction. The ultrasound initially Este trabajo está dirigido a la evaluación de diferentes increases DRE of PCBs by 8 % after 10 min of reaction parámetros por el tratamiento de PCBs presente en el time. After a reaction time of 120 min no difference in DRE aceite de transformador Sovtol-10 mediante el proceso de was measured when using ultrasound. descloración química con el alcóxido del polietilenglicol (KPEG). Utilizando KOH en perlas fue determinado prime- Keywords: Polychlorinated biphenyls, dechlorination, ramente el efecto de la relación en peso de KPEG/aceite, KPEG process, sovtol, ultrasound. la relación molar KOH/PEG y el peso molecular del polieti- lenglicol. La influencia de otros dos parámetros: el KOH en polvo y el ultrasonido fue investigada con los valores óp- RESUM timos obtenidos del experimento anterior. Los resultados se calcularon en términos de eficiencia en la destrucción – Aquest treball està dirigit a l’avaluació de diferents pa- eliminación de PCBs (DRE). Una reducción del 93.7 % en ràmetres pel tractament de PCBs presents en l’oli de el % de DRE fue obtenido bajo las siguientes condiciones transformador Sovtol-10 utilitzant la descloració química experimentales: PEG 400, relación en peso KPEG/aceite amb l’alcòxid del polietilenglicol (KPEG). Al utilitzar KOH de = 30 y relación molar KOH/PEG = de 2 para dos horas en perles es va determinar primerament l’efecte de la re- de reacción. A los 10 minutos de reacción el ultrasonido lació en pes de KPEG/oli, la relació molar KOH/PEG i el incrementa el DRE en un 8 %. Después de los 120 minu- pes molecular del polietilenglicol. La influència dels dos tos de reacción no hay diferencias significativas en el DRE paràmetres: el KOH en pols i el ultrasò va ser investigada cuando utilizamos el ultrasonido. amb els valors òptims obtinguts de l’experiment anterior. Els resultats es van calcular en termes d’eficiència en la Palabras claves: Bifenilos policlorados, descloración, destrucció-eliminació de PCBs (DRE). Una reducció del proceso KPEG, sovtol, ultrasonido. 93.7% en el % d’DRE va ser obtingut sota les següents condicions experimentals: PEG 400, relació en pes KPEG /oli = 30 i relació molar KOH/PEG = 2 per a dues hores SUMMARY de reacció. Als 10 minuts de reacció l’ultrasò incrementa el DRE a un 8%. Després dels 120 minuts de reacció no Different parameters for the treatment of PCBs present in hi ha diferències significatives en el DRE quan utilitzem el transformer oil (Sovtol-10) using chemical dechlorination ultrasò. with polyethylene alkoxide (KPEG) were evaluated. The effect of the KPEG/oil weight ratio, KOH/PEG mole ratio Paraules claus: bifenils policlorats, descloració, procés and polyethylene glycol molecular weight (PEG) using KPEG, sovtol, ultrasò. KOH in pellets were determined first. With the optimal va- lues obtained the influence of two other parameters: KOH in powder and ultrasound was investigated. The overall dechlorination performance was assessed in terms of the *Corresponding author: [email protected]; Tel.: (53) destruction and removal efficiency (DRE) of PCBs. Avera- (42)-281510. Fax: (53) (42)-81608 ge DRE of 93.7 % was obtained under the following condi- 206 AFINIDAD LXX, 563, Julio - Septiembre 2013 INTRODUCTION (UNEP, 2004). This incineration technology is effective for destruction of PCB; however, it is hampered by the costs Polychlorinated biphenyls (PCBs) are amongst the world’s of disposal and the exclusion of reusable materials as well most widespread hazardous environmental contaminants. as measures that have to be taken to avoid production They have been detected in most environments (indoor and emission of highly toxic products such as dibenzo- and outdoor atmospheres, surface and subsurface waters, p-dioxins (PCDD) and dibenzofurans (PCDF). Some other soils and foodstuffs). Relatively considerable quantities of alternative techniques seem viable, environmentally ac- PCBs have been, and continue to be, released into the ceptable and cost-competitive for reducing of PCBs con- environment due to inadequate draining practices, losses centration in many selected wastes (Rahuman et al., 2000). and accidental spills in a wide range of industrial installa- For that reason different methods for the destruction of tions (UNEP, 2002). PCBs have been proposed such as wet-air oxidation (Yak The term of polychlorinated biphenyls makes reference to et al., 2000), super or supra-critical oxidation (Sako et al., a class of synthetic organic products called chlorinated 1999; Anitescu and Tavlarides, 2000), photolysis in the hydrocarbons. Theoretically there are 209 PCBs conge- presence of hydrogen donors and oxidants (Wong and ners but only about 130 congeners are found in commer- Wong, 2006), electrolytic reduction (Matsunaga and Ya- cial products. The PCBs internationally commercialized suhara, 2002) and a number of other chemical methods, are a mixture of congeners that have been chlorinated to based on laboratory experiments only. different degrees, according to its final use. Their excellent Wu (Wu et al., 2005) applied a practical and efficient dis- stability and thermal properties make PCBs suitable as a posal method for hydrodechlorination of polychlorinated heat transfer medium and dielectric liquids in electrical biphenyls (PCBs) in transformer oil. Transformer oil con- transformer and capacitors. Later, PCBs are considered taining PCBs was treated by nanometric sodium hydride as Persistent Organic Contaminants; they remain in the (nano-NaH) and transition metal catalysts. High destruc- environment for long periods and are included in the “Dirty tion and removal efficiency (89.8 %) can be attained by Dozen”, a list of the twelve most hazardous contaminants nano-NaH alone under mild conditions. The process exhi- known (UNEP, 1999). bits apparent characteristics of a first order reaction. In Cuba, the principal use of PCBs is largely concentrated Literature search reveals that papers about the polyethyle- in electrical transformers and capacitors. These are insta- ne glycol (PEG)/base chemical process are rather uncom- lled indistinctly, according to its necessity, in the electrical mon, although the process appears promising from an grids that supply power to the residential, industrial and industrial point of view (De Filippis et al., 1997; Lopera commercial production sectors. The Department of Power and Aguirre, 2006; Ryoo et al., 2007). These processes are Supply of the Ministry of Basic Industry owns and opera- based on the reaction between PCBs and PEG alkoxide, a tes approximately 90 % of the existing electrical transfor- group of reagents generically referred to as “APEG” (alkali mers throughout the country, but other sectors own and metal polyethylene glycolate) has been developed. operate entirely imported industrial PCBs containing equi- Brunelle (Brunelle, 1982) carried out an extensive study of pment as well. Aroclor 1260 dechlorination in such non-polar media as Until now, no technology for the treatment of electrical heptane and toluene and found that PCBs react with po- equipment containing PCBs is available in Cuba. As a lyethylene glycols and potassium hydroxide (KPEG) under result of the ever increasing stocks of these equipment’s mild conditions, following a simple nucleophilic substitu- being taken out of service, the national strategy has been tion by a polyethylene glycol alkoxide, probably occurring the temporary confinement under specific criteria that en- in the glycol phase. De Filippis (De Filippis et al., 1982; sures the lowest risks possible to health and the environ- 1999) applied the same chemical process to remove PCBs ment. PCBs containing oil known as Sovtol-10 constitutes from contaminated dielectric and lube oils, concluding that 62.1 % of the quantities of fluid used in Cuba. The princi- the former are easier to dehalogenate. First-order kinetic pal origin of the import was the former USSR up to a few was observed for each PCB as well as with respect to the years ago (CITMA, 2004). PEG concentration. The reaction was also affected by the In the former USSR, PCBs were first synthesized in 1934 KOH/PEG ratio. In all studies mentioned treatment was and industrial production was launched in 1939 and bet- performed on oil samples contaminated with PCB at levels ween 1987 and 1993 production of PCBs in Russia was less than 1 g/kg. terminated. In this period technical mixtures of PCBs were To our knowledge there are no studies treating transfor- produced mainly at Russia territory but also in Kazakhstan, mer oil with high PCBs concentrations using the KPEG Armenia, Uzbekistan and Ukraine (Amirova et al., 2001). process. Only Kaštánek and Kaštánek (Kaštánek and There are three different mixtures of Sovol (a mixture of Kaštánek, 2005) use PCBs concentrations in the order mainly tetra- and pentachlorinated PCBs) and trichloro- of 15 g/kg of oil (sum of seven indicative congeners) but benzenes (TCBZ). Sovtol-1 is composed of 75 % Sovol using the modified KPEG process with powdered alumi- and 25 % TCBZ; Sovtol-2 has 64 % of Sovol and 36 % num at higher temperatures. This process has drawbacks TCBZ, and Sovtol-10, 90 % of Sovol and 10 % TCBZ because requires inert atmospheres and extensive tempe- (Wyrzykowska et al., 2006). The dielectric oil that contains rature control.