Moises Teles dos Santos

Moisés Teles dos Santos*, Pablo Morgavi and Galo A.C. Le Roux
The Amazon region has richness of oleaginous plants that have attracted attention due to its unique properties. Integrating local communities in an economic chain of valorization of fats/oils can enhance the social dimension of local oleaginous industry sustainability. Given the large diversity of raw materials and the possibility to mix them in different proportions, an experimental effort must be done to
evaluate the physical properties of such feedstocks. In this context, the development of computational tools able to estimate physical properties based on rigorous thermodynamic models can orient the experimental efforts thorough the mixtures of fats and oils most promising. The evaluation of the melting curves of nine Amazonian oils and fats is done by using thermodynamic modeling of the solid-liquid equilibrium and optimization tools. The binary blends of different raw materials were also evaluated.

Gerbaud, V. ; TELES DOS SANTOS, M. ; PANDYA, N. ; AUBRY, J.M.
We investigate the use of computer aided molecular design (CAMD) approach for enhancing the properties of existing molecules by modifying their chemical structure to match target property values. The activity of tailoring molecules requires to aggregate knowledge disseminated across the whole chemical enterprise hierarchy, from the manager level to the chemists and chemical engineers, with different backgrounds and perception of what the ideal molecule should be. So, we propose a framework that allows the search to be successful in matching all requirements while capitalizing this knowledge spread among actors with different backgrounds with the help of SBVR (Semantics of Business Vocabulary and Rules) and OCL (Object Constraint Language). In the context of using biomass as the feedstock, we discuss the coupling of CAMD tools with computer aided organic synthesis tools so as to propose enhanced bio-sourced molecules which could be synthesized with eco-friendly pathways. Finally, we evaluate the sustainability of the molecules and of the whole decision-process as well. Specific applications that concern the use of bio-sourced molecules are presented: a case of typical derivatives of chemical platform molecules issued from the itaconic acid to substitute N-methyl-2-pyrrolidone NMP or dimethyl-formamide DMF solvents and a case of derivatives of lipids to be used a biolubricants.

TELES DOS SANTOS, M.; VIANA, Í. S. ; RACT, J.N.R. ; Le Roux, G.A.C
In order to evaluate thermal properties of fats and oils for product design, palm stearin, canola oil and fully hydrogenated soybean oil blends were studied. The fatty acids composition (by gas chromatography), the regiospecific distribution of saturated, monounsaturated and polyunsaturated fatty acids (by Nuclear Magnetic Resonance), the softening point and thermal transitions (by differential scanning calorimetry) were measured experimentally. Iodine value and saponification value were calculated using experimental fatty acids composition. Thermodynamic modeling (Solid-liquid Equilibrium) and computational simulations of solid-liquid transitions were used to predict the Solid Fat Content (SFC) of blends with all possible mass fraction of each oil at 0 °C and 25 °C and to predict changes in heat capacity of the mixtures in the whole melting range. The computational predictions were able to identify the correlation between the amount of saturated fatty acids and melting profile, offering quantitative insights for the whole ternary diagram. The experimental DSC curves, in average, showed more peaks than the predicted curves, due to the use of equilibrium hypothesis by the model and the presence of kinetics factor in experimental DSC.

DOS SANTOS, MOISÉS TELES; GERBAUD, VINCENT ; LE ROUX, GALO A.C
Despite the greater attention given to biofuels application in the literature, there are many economic and environmental drivers to use vegetables oils (VOs) as a renewable feedstock for other applications. These drivers are discussed in the present work and the technological challenges imposed by this shift towards new VOs uses are also discussed. They are mainly associated to the reaction routes issues, the performance regarding end-user properties, experimental procedures and property prediction models. The need for more holistic approaches (life cycle analysis) is briefly discussed and the potential benefits arising from new computer-aided tools are highlighted as well.

TELES DOS SANTOS, M.; Gerbaud, V. ; ROUX, G.A.C. LE
A Solid–Liquid Equilibrium model coupled with an algorithm for direct minimization of the Gibbs free energy function was used to compute the melting profiles for binary blends of vegetable oils. The effect of interesterification on the Solid Fat Content (SFC) is simulated by using a completely random distribution of fatty acids on the glycerol structures. The methodology was applied to different blends of 6 vegetable oils: canola oil, fully hydrogenated palm oil stearin, palm oil stearin, cottonseed oil, milkfat and corn oil. The predicted results were compared with experimental data from literature and the average absolute error in SFC was 3.33% (physical mixture without interesterification) and 4.13% (after interesterification). Additionally, two qualitative aspects also observed in experimental works could be computationally detected: the existence of temperatures in which the blends have the same SFC before and after reaction and the fact that randomized blends tend to melt at lower temperatures than their corresponding mixtures. The results reinforced the potential use of computer-based tools to explore new formulations aiming to match a desired melting range, reducing the experimental efforts in product design where vegetable oils are used and the thermal profile has a fundamental role