Pretreatment of lignocellulosic materials is essential for bioconversion because of the various physical and chemical barriers that greatly inhibit their susceptibility to bioprocesses such as hydrolysis and fermentation. The aim of this article is to review some of the most important pretreatment methods developed to date to enhance the conversion of lignocellulosics. Steam explosion, which precludes the treatment of biomass with high-pressure steam under optimal conditions, is presented as the pretreatment method of choice and its mode of action on lignocellulosics is discussed. The optimal pretreatment conditions for a given plant biomass are defined as those in which the best substrate for hydrolysis is obtained with the least amount of soluble sugars lost to side reactions such as dehydration. Therefore, pretreatment optimization results from a compromise between two opposite trends because hemicellulose recovery in acid hydrolysates can only be maximized at lower pretreatment severities, whereas the development of substrate accessibility requires more drastic pretreatment conditions in which sugar losses are inevitable. To account for this heterogeneity, the importance of several process-oriented parameters is discussed in detail, such as the pretreatment temperature, residence time into the steam reactor, use of an acid catalyst, susceptibility of the pretreated biomass to bioconversion, and process design

Lignocellulosic biomasses are primarily composed of cellulose, hemicelluloses and lignin and these biopolymers are bonded together in a heterogeneous matrix that is highly recalcitrant to chemical or biological conversion processes. Thus, an efficient pretreatment technique must be selected and applied to this type of biomass in order to facilitate its utilization in biorefineries. Classical pretreatment methods tend to operate under severe conditions, leading to sugar losses by dehydration and to the release of inhibitory compounds such as furfural (2-furaldehyde), 5-hydroxy-2-methylfurfural (5-HMF), and organic acids. By contrast, supercritical fluids can pretreat lignocellulosic materials under relatively mild pretreatment conditions, resulting in high sugar yields, low production of fermentation inhibitors and high susceptibilities to enzymatic hydrolysis while reducing the consumption of chemicals, including solvents, reagents, and catalysts. This work presents a review of biomass pretreatment technologies, aiming to deliver a state-of-art compilation of methods and results with emphasis on supercritical processes.