Combustion Science and Technology, Vol.179, No.5, 987-1001, 2007
Evaluation of organometallic fuel additives for soot suppression
In this work, we investigate the utility of the smoke lamp for evaluating the soot-reducing potential of additives, by comparing it to a more complex liquid-fed laminar diffusion flame. The additives, ferrocene (bis(cyclopentadienyl) iron-Fe(C5H5)(2)), ruthenocene (bis(cyclopentadienyl)ruthenium-Ru(C5H5)(2)), iron naphthenate (a 12% iron salt of naphthenic acid, which is a mixture of fatty carboxylic acids, some of which may include a cyclopentane ring), and MMT (Methylcyclopentadienyl manganese tricarbonyl-CH3C5H4Mn(CO)(3)) are evaluated at various concentrations in the jet fuel JP-8. Although the smoke lamp is a simple, inexpensive, and widely-available test for evaluating the sooting potential of liquid fuels, it does not provide an effective measure of soot suppression by metal-containing additives. The drop-tube reactor more accurately captures the physical conditions and processes-droplet vaporization, ignition, and rich vs. lean operation-typically found in more complex systems. We find in the smoke lamp that ferrocene, and to a lesser degree ruthenocene, are effective soot suppressors when used in JP-8, and that their effectiveness increases with increasing concentration. In the smoke lamp, MMT and iron naphthenate have minimal effect. On the other hand, in the drop-tube reactor, all four additives are quite effective, especially at fuel lean conditions, where soot suppression reaches 90-95%. Under fuel-rich conditions, where in some cases the additives elevate the yield of soot aerosol slightly, we find a significant increase in the production of the soluble organic fraction of the aerosol, i.e., tar. In order to understand why the smoke lamp sometimes fails to indicate a soot suppressing potential (i.e., from MMT and iron naphthenate), soot samples were collected from a wick lamp burning ferrocene and iron naphthenate additives in JP-8. These samples, as well as several from the drop-tube reactor, were analyzed by X-Ray Fluorescence (XRF) in order to determine their metal content, and we find that the soot aerosol produced by the wick lamp using ferrocene-containing fuel had roughly 30 times the iron content of the soot aerosol produced by the wick lamp using iron-naphthenate-containing fuel. This difference in metal content is not found in samples produced in the drop-tube reactor. We conclude that the poor performance of iron naphthenate in the smoke lamp is likely the result poor vaporization of the additive from the wick, a consequence of its high molecular weight (average 465).