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Reducing the Carbon Footprint of Fuels and Petrochemicals – Alternative Feedstocks and Innovative Technologies

DGMK Conference October 8 - 10, 2012, Berlin, Germany

High Efficiency Esterification and Transesterification of Alternative Feedstock for Biodiesel Production

D.C. Boffito*, S.Mansi*, C. Pirola*, J-M. Leveque**, G. Carvoli***, S. Vitali*C.L. Bianchi*,

A. Rispoli****, D. Barnabè****, R. Bucchi****

*Università degli Studi di Milano – Dipartimento di Chimica Fisica ed Elettrochimica, Milano, Italy, **University of Savoie-LCME/CISM, Le Bourget du Lac cedex, France

***Khemistar S.r.l.-P., Novara, Italy, ****Agri2000 Soc. Coop., Castel Maggiore (BO), Italy, Abstract

The use of non-food, raw oils for fatty alkyl methyl esters (FAME) production, i.e. biodiesel, requires several standardization processes. The search for high efficiency transformation methods is therefore a key issue in this context. In this work several non-edible oils such as waste cooking oil (alone or in blends) and oils from alternative crops (e.g. Brassica juncea, Nicotiana tabacum, Cartamus tinctorius) have been selected to be processed to FAME.

All the oils were first deacidified through esterification of the FFA (Free Fatty Acids) to yield FAME and then transformed into biodiesel by transesterification.

The FFA esterification was catalyzed using ion exchange resins (Purolite®D5081, Amberlyst®15 and Amberlyst®46). All the selected feedstock can be successfully deacidified by FFA esterification in very mild conditions (336 K) and within 2 hours using ion exchange resins, reaching FFA conversions up to 95%. Very high quality biodiesel was obtained from all the oils deacidified with this method, so avoiding any costly distillation step. D5081 and A46 demonstrated high stability over several hours under esterification operating conditions, due their surface functionalization which confers pseudo-homogenous properties to the reacting system avoiding mass transfer limitations. This aspect is very important to match compliance with industrial requirements.

Esterification and transesterification catalyzed by A46 and KOH, respectively, were investigated also with the use of ultrasound (US). High temperatures and pressures caused by the acoustic cavitation in various reacting systems have been widely proven to bring benefits both to homogeneous and heterogeneous systems.

Our study shows how the use of US (20kHz) adopted in the esterification reaction brings to a slight increase in the FAME yields when conducted at temperatures lower than the traditional process (303 K), while does not bring to any advantage when used at 336 K. Acoustic cavitation effects are in fact enhanced at lower temperatures. This is worthy in particular for heterogeneous systems, whereby the temperature control is more difficult.

The use of the US in the homogeneous transesterification shows how at lower temperatures (303 K) and considerably shorter times (30 min) FAME yields comparable to the ones achieved by the traditional process (333 K, 150 min) are obtained. In particular, yields up to 85% were already obtained after 5 minutes of reaction using a continuous reactor. The very high yields achieved are due to the positive effects brought by the acoustic cavitation.

For this study sonochemical reactors provided and patented by Synetude SAS (Chambery, France) were used.

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 Supercritical Fluid Extraction 25_Boffito.pdf Page 001
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