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DatoValore
TitleTHE GAS PHASE DECOMPOSITION OF SYNTETIC LUBRICANTS UNDER PYROLYTIC CONDITIONS
AbstractThis paper deals with the gas phase thermal degradation, under pyrolytic conditions, of three commercial industrial lubricants, using the system for thermal diagnostic studies (STDS) apparatus between 400 and 1000 oC. Two lubricants of different triaryl phosphates composition and one based on fatty acid methyl-ethyl esters have been studied in order to investigate their behavior in simulated "hot spot" conditions. The main objective of the work was to verify the thermal stability of the three samples and to determine the products generated during the thermal exposure as a function of the experimental conditions. The occurrence of hazardous by-products was investigated as well as their composition and evolution as a function of temperature. Experimental results show that, for each sample tested, the degradation starts at 600-700 oC and is complete within 900 and 1000 oC. A great number of by-products, mainly aromatic and poly-aromatic compounds (PAHs), was always observed at temperatures higher than 700 oC. Two mechanisms are proposed for the formation of these products: the first one is directly related to the production of benzene radicals originated from aryl moieties, that act as building blocks in consecutive reactions; the second one is related to the occurrence of displacement and cyclization reactions which lead to the obtainment of aromatic moieties from vinyl radicals. The amount of PAHs coming from the lubricant based on fatty acid methyl-ethyl esters is always much lower than that of the other two samples. Moreover, the pyrolysis of the two triaryl phosphates lubricants leads to the formation of three phosphorus-containing aromatic by-products (phosphabenzene, isophosphinoline and phosphinoline) and a mechanism for their formation was proposed. On the basis on the experimental results found, it is possible to conclude that the lubricant based of fatty acid methyl-ethyl esters produces less hazardous by-products than triaryl-phosphates ones when exposed to thermally severe pyrolytic conditions.
SourceJournal of analytical and applied pyrolysis (Print) 71 (1), pp. 165–178
JournalJournal of analytical and applied pyrolysis (Print)
EditorElsevier, Tokyo, Paesi Bassi
Year2004
TypeArticolo in rivista
DOI10.1016/S0165-2370(03)00084-6
AuthorsMASCOLO G.(a); RAUSA R. (b); MININNI G. (c); TINUCCI L. (b)
Text42219 2004 10.1016/S0165 2370 03 00084 6 ISI Web of Science WOS 000220881800012 THE GAS PHASE DECOMPOSITION OF SYNTETIC LUBRICANTS UNDER PYROLYTIC CONDITIONS MASCOLO G. a ; RAUSA R. b ; MININNI G. c ; TINUCCI L. b a C. N. R. Istituto di Ricerca sulle Acque, Via F. De Blasio 5, 70123 Bari, Italy; b EniTecnologie S.p.A., Via Maritano 26, 20097 S. Donato Milanese, Milan, Italy; c C. N. R. Istituto di Ricerca sulle Acque, Via Reno 1, 00198 Rome, Italy This paper deals with the gas phase thermal degradation, under pyrolytic conditions, of three commercial industrial lubricants, using the system for thermal diagnostic studies STDS apparatus between 400 and 1000 oC. Two lubricants of different triaryl phosphates composition and one based on fatty acid methyl ethyl esters have been studied in order to investigate their behavior in simulated hot spot conditions. The main objective of the work was to verify the thermal stability of the three samples and to determine the products generated during the thermal exposure as a function of the experimental conditions. The occurrence of hazardous by products was investigated as well as their composition and evolution as a function of temperature. Experimental results show that, for each sample tested, the degradation starts at 600 700 oC and is complete within 900 and 1000 oC. A great number of by products, mainly aromatic and poly aromatic compounds PAHs , was always observed at temperatures higher than 700 oC. Two mechanisms are proposed for the formation of these products the first one is directly related to the production of benzene radicals originated from aryl moieties, that act as building blocks in consecutive reactions; the second one is related to the occurrence of displacement and cyclization reactions which lead to the obtainment of aromatic moieties from vinyl radicals. The amount of PAHs coming from the lubricant based on fatty acid methyl ethyl esters is always much lower than that of the other two samples. Moreover, the pyrolysis of the two triaryl phosphates lubricants leads to the formation of three phosphorus containing aromatic by products phosphabenzene, isophosphinoline and phosphinoline and a mechanism for their formation was proposed. On the basis on the experimental results found, it is possible to conclude that the lubricant based of fatty acid methyl ethyl esters produces less hazardous by products than triaryl phosphates ones when exposed to thermally severe pyrolytic conditions. 71 The gas phase decomposition of synthetic lubricants under pyrolytic conditions 2004_J_An_Appl_Pyrolysis.pdf Articolo in rivista Elsevier 0165 2370 Journal of analytical and applied pyrolysis Print Journal of analytical and applied pyrolysis Print J. anal. appl. pyrolysis Print Journal of analytical and applied pyrolysis. Print International symposium on analytical and applied pyrolysis Print giuseppe.mininni MININNI GIUSEPPE giuseppe.mascolo MASCOLO GIUSEPPE