Optimization of biodiesel production from corn oil by methanolysis catalyzed by corn cob ash

Abstract

The use of low-cost or priceless feedstocks such as byproducts in biodiesel production results in a reduced overall process costs. The present paper reports the use of corn germs and corn cobs as byproducts from corn-based starch production in the biodiesel production by the methanolysis of the oil extracted from corn germs, catalyzed by the ash produced by combustion of corn cobs. The major aim was to optimize the methanol-to-oil molar ratio, catalyst loading, and reaction time in a batch stirred reactor with respect to the content of methyl ester fatty acids (FAME). The statistical modeling and optimization were carried out using a second-order polynomial (quadratic) model developed by the response surface methodology combined with a 33 factorial design with 3 central points. The FAME content was determined by a high-pressure liquid chromatography method. The analysis of variance showed that only the catalyst amount, the reaction time, the catalyst amount interaction with reaction time and all three quadratic terms were the significant model terms with the confidence level of 95 %. The optimum reaction conditions (the catalyst amounts of 19.8 %, the methanol-to-oil molar ratio of 9.4 mol/mol and the reaction time of 31 min) provided the FAME content of 98.1 %, which was in an excellent agreement with the predicted FAME content (98.4 %). Thus, both corn germs and corn cobs may be suitable feedstocks for biodiesel production.

Upotreba jeftinih ili bezvrednih sirovina, kao što su sporedni proizvodi, u proizvodnji biodizela ima za rezultat smanjene ukupne troškove procesa. U ovom radu su prikazani rezultati upotrebe kukuruznih klica i okrunjenog kukuruznog klipa (kurdeljke, krudeljke) kao sporednih proizvoda iz proizvodnje kukuruznog skroba u proizvodnji biodizela metanolizom ulja izdvojenog iz kukuruznih klica, katalizovane pepelom dobijenim sagorevanjem kurdeljke. Glavni cilj je bila optimizacija molskog odnosa metanol-ulje, količine katalizatora i reakcionog vremena u šaržnom reaktoru sa mešanjem u odnosu na sadržaj metilestra masnih kiselina (MEMK). Statističko modelovanje i optimizacija izvršeni su korišćenjem kvadratnog modela, razvijenog metodologijom odzivne površine, u kombinaciji sa 33 faktorijelnim planom sa 3 centralne tačke. Sadržaj MEMK-a je određen metodom tečne hromatografije pod visokim pritiskom. Analiza varijanse je pokazala da su samo uticaji količine katalizatora, reakcionog vremena, interakcije količine katalizatora sa reakcionim vremenom i sva tri kvadratna člana statistički značajni sa nivoom pouzdanosti od 95 %. Pod optimalnim reakcionim uslovima (količina katalizatora 19,8 %, molski odnos metanol/ulje 9,4 mol/mol i reakciono vreme 31 min) dobijen je sadržaj MEMK-a od 98,1 %, koji se slaže sa predviđenim sadržajem MEMK-a (98,4 %). Prema tome, i kukuruzne klice i kurdeljka mogu biti pogodne sirovine za proizvodnju biodizela.