The reduction of oil resources and the consequent increasing price of oil distillates as well as the environmental concerns of conventional fuels has renewed and increased interest on the preparation of biofuels from renewable resources. One of those interests is nowadays focused on biodiesel, which is usually prepared from crude and refined triglyceride containing raw materials, such as vegetable oils, animal fats and wastes—for instance waste cooking oil and yellow and brown grease. Since several commercial interests converge on this kind of feedstock, one of the priorities being crops for human food supply, the research efforts on biodiesel production are diverting towards the use of low quality triglyceride-containing raw materials. Nevertheless, all of these feedstocks feature high water and free fatty acids (FFAs) content, which strongly affects the behaviour of conventional homogeneous base catalysts. These catalysts are primarily NaOH and KOH, but also NaOCH₃ and KOCH₃ are employed—as solutions in methanol—mainly in large-scale production plants. In this context, an appropriate solid acid catalyst which could simultaneously carry out esterification of FFAs and transesterification of triglycerides would be of great interest for biodiesel production. Moreover, a heterogeneous acid catalyst could be easily incorporated into a packed bed continuous flow reactor, simplifying product separation and purification and reducing waste generation. The present review attempts to provide a wide overview on the possibility of heterogeneous acid catalysts for biodiesel production replacing the homogeneous conventional process. In this way, three aspects of solid acid catalysis for biodiesel production will be reviewed. The first section deals with the solid acid-catalyzed esterification of FFAs, the second topic relates to the transesterification of triglycerides, while the third deals with solid acid-catalyzed transformation of bioglycerol into oxygenated compounds for biodiesel formulation.

SBA-15 mesoporous silica has been functionalized with arenesulfonic acid groups by means of a one-step simple synthesis approach involving co-condensation of tetraethoxysilane (TEOS) and 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (CSPTMS) in the presence of a poly(alkylene oxide) block copolymer (Pluronic 123) under acid silica-based catalysis. The resultant materials show hexagonal mesoscopic order and pores sizes up to 60 Å, with acid exchange capacities of ca. 1.3 mequiv. H⁺ per g SiO₂ and surface areas up to 600 m² g⁻¹. The sulfonic groups anchored to the silica surface of the pore walls are thermally stable to temperatures up to 380 °C and resistant to leaching in organic and aqueous solutions under mild conditions. ³¹P MAS NMR measurements of chemically adsorbed triethylphosphine oxide and the catalytic properties confirm the presence of Brönsted acid centers in these mesoporous materials containing arenesulfonic acid groups that are stronger than those found in propanesulfonic-modified SBA-15 and Al-MCM-41.

Sulfonic acid-functionalized mesostructured silicas have demonstrated excellent catalytic behaviour in the acetalisation of glycerol with acetone to yield 2,2-dimethyl-1,3-dioxolane-4-methanol, also known as solketal. This molecule constitutes an excellent compound for the formulation of gasoline, diesel and biodiesel fuels. The activity achieved with arenesulfonic acid-functionalized silica is comparable to that displayed by Amberlyst-15. Optimal production of solketal over arenesulfonic acid mesostructured silica has been established for a reaction system consisting of three consecutive 2-step batches (30 min under reflux and an evaporation step under vacuum), and using a 6/1 acetone/glycerol molar ratio. The use of lower grades of glycerol, such as technical (purity of 91.6 wt%) and crude (85.8 wt%) glycerol, has also provided high conversions of glycerol over sulfonic acid-modified heterogeneous catalysts (84% and 81%, respectively). For refined and technical glycerol the catalysts have been reused, without any regeneration treatment, up to three times, keeping the high initial activity. However, the high sodium content in crude glycerol deactivates the sulfonic acid sites by cation exchange. This deactivation is readily reversed by simple acidification of the catalyst after reaction.