This work aimed to compare two different catalysts in the production of a long chain ketone, intermediate in the production of hydrocarbons, during pyrolysis of tetradecanoic acid as a model fatty acid. The studied variables were the temperature, 450 and 600 ºC, and catalysts, γ-Al2O3 and Nb2O5, the latter has never been studied under such conditions. Pyrolysis experiments were performed in a micro-pyrolyzer coupled to a gas chromatograph with mass spectrometry detector (GC-MS). In all pyrolysis conditions, 14-heptacosanone was formed in varied amounts. Under the best conditions, for pyrolysis at 600 ºC, using γ-Al2O3 as catalyst, the yield of 14-heptacosanone was 18% and the yield of hydrocarbons 24%. The major hydrocarbon product obtained was 1-dodecene. Among the partially deoxygenated compounds, the main products were the ketones 14-heptacosanone and 2-pentadecanone. The present experimental work confirmed also the possibility to obtain hydrocarbons having a chain length longer than the chain length of the original fatty acid reagent, due to a ketonization route followed by decarbonylation.

Three different microalgae species, Desmodesmus sp., Nannochloropsis oculata and Halamphora coffeaeformis were grown under controlled conditions. The resulting dry biomass was characterized by TG-DTA (thermogravimetry-differential thermal analysis) and extracted with three solvents having different polarities. The extracts gross mass yields varied from 2% using n-hexane to 23% (or 74% when subtracting the volatiles and ashes) when using methanol-chloroform whatever the microalgae species. Fourier transform infrared (FTIR) spectra of all extracts suggested the presence of fatty esters and acids. The extracts were pyrolyzed at 600 °C, using a micro pyrolizer coupled to a gas chromatograph-mass spectrometer (GC-MS), without and with g-alumina as catalyst. Hydrocarbons concentrations varied respectively from 92% in the better case to 46% in the worst case. The C9-C15 fraction of these hydrocarbons, potentially useful for biokerosene formulation, was object of detailed analysis. In this fraction, nitrogenous products had concentrations always lower than 0.1%. The main hydrocarbons produced were linear 1-alkenes for thermal pyrolysis whereas for pyrolysis with g-alumina, linear 1-alkenes and also alkenes isomers and linear alkanes, together with cyclic and aromatic compounds were observed for all microalgae species, but in different proportions. The C9-C15 fraction of pyrolyzed extracts can be considered as precursor for biokerosene or direct “drop in” fuel for kerosene petroleum fraction.

A pirólise rápida do ácido oleico foi estudada sobre catalisadores com 10% Ni suportados em sílica e alumina. Os catalisadores foram impregnados com 10% m/m de ácido oleico. Os precursores secos e os catalisadores contendo ácido oleico foram caracterizados por análise termogravimétrica. Os catalisadores calcinados foram analisados por difração de raios X (XRD) e redução à temperatura programada (TPR). As amostras com ácido oleico adsorvido foram submetidos à pirólise rápida a 650 °C. A pirólise de ácido oleico puro levou a 10% de conversão, enquanto a pirólise catalítica resultou em praticamente completa conversão. O catalisador NiO/alumina produziu mais hidrocarbonetos do que o NiO/sílica. Os principais produtos obtidos com NiO/sílica foram 1-alcenos, enquanto que os principais produtos obtidos com NiO/alumina foram isômeros de alcenos e aromáticos, e pequenas quantidades de compostos oxigenados, principalmente álcoois. A pirólise rápida de ácido oleico adsorvido em catalisadoras representa um método útil para distinguir as propriedades dos catalisadores e suas diferentes atividades.

Flash pyrolysis of oleic acid was studied over 10 wt.% nickel catalysts supported on silica and alumina. The catalysts were impregnated with 10 wt.% oleic acid. The dried precursors and the catalysts containing oleic acid were characterized by thermogravimetric analysis. The calcined catalysts were analyzed by X-ray diffraction (XRD) and temperature programmed reduction (TPR). Samples containing adsorbed oleic acid were submitted to flash pyrolysis up to 650 °C. Whereas pyrolysis of oleic acid without catalyst converted only about 10%, the pyrolysis of oleic acid adsorbed on catalysts allowed practically a complete conversion. NiO/alumina yielded a higher amount of liquid hydrocarbons than NiO/silica. The main products obtained with NiO/silica were 1-alkenes, whereas the main products obtained with NiO/alumina were alkene isomers and aromatics. Small amounts of oxygenated compounds were also observed, principally alcohols. The flash pyrolysis of oleic acid adsorbed on different catalyst surfaces appears as a useful way to distinguish activity trends of different catalyst samples.

Os processos industriais mais utilizados na produção de combustíveis líquidos semelhantes ao diesel usam catalisadores homogêneos básicos através das metanólise e etanólise de óleos tais como os de soja, canola, palma entre outros. Desse modo, se obtém o biodiesel. Por sua vez, transformações termo-catalíticas usando as facilidades existentes nas refinarias de petróleo são alternativas que merecem atenção devido a sua viabilidade econômica. De fato, três processos industriais já estão em funcionamento e novos projetos estão em fase final para comercialização. O presente trabalho analisa os experimentos já realizados por pesquisadores brasileiros nas áreas do craqueamento, do craqueamento catalítico e do hidrocraqueamento catalítico dos óleos vegetais puros ou modificados. A partir dos resultados descritos, são sugeridas novas direções destas pesquisas para os próximos anos.

The most used industrial processes for the production of liquid fuels like diesel type are based on the methanolysis and ethanolysis of various oil reactants, such as palm, soybean and rapeseed oils, in the presence of homogeneous base catalysts. However, thermal and catalytic transformations of vegetable oils using available reactors and industrial processes are possible alternatives and deserve attention. In fact, three industrial processes are operating and new projects are announced. The present work analyses the experimental studies performed up to now by Brazilian researchers in the field of cracking, catalytic cracking and hydrocracking of pure or modified vegetable oils. From the published results, some research areas for the near future are suggested.