Lignocelluloses are often a major or sometimes the sole components of different waste streams from various industries, forestry, agriculture and municipalities. Hydrolysis of these materials is the first step for either digestion to biogas (methane) or fermentation to ethanol. However, enzymatic hydrolysis of lignocelluloses with no pretreatment is usually not so effective because of high stability of the materials to enzymatic or bacterial attacks. The present work is dedicated to reviewing the methods that have been studied for pretreatment of lignocellulosic wastes for conversion to ethanol or biogas. Effective parameters in pretreatment of lignocelluloses, such as crystallinity, accessible surface area, and protection by lignin and hemicellulose are described first. Then, several pretreatment methods are discussed and their effects on improvement in ethanol and/or biogas production are described. They include milling, irradiation, microwave, steam explosion, ammonia fiber explosion (AFEX), supercritical CO₂ and its explosion, alkaline hydrolysis, liquid hot-water pretreatment, organosolv processes, wet oxidation, ozonolysis, dilute- and concentrated-acid hydrolyses, and biological pretreatments.

Lignocelluloses are widely investigated as renewable substrates to produce biofuels, e.g., ethanol, methane, hydrogen, and butanol, as well as chemicals such as citric acid, lactic acid, and xanthan gum. However, lignocelluloses have a recalcitrance structure to resist microbial and enzymatic attacks; therefore, many physical, thermal, chemical, and biological pretreatment methods have been developed to open up their structure. The efficiency of these pretreatments was studied using a variety of analytical methods that address their image, composition, crystallinity, degree of polymerization, enzyme adsorption/desorption, and accessibility. This paper presents a critical review of the first three categories of these methods as well as their constraints in various applications. The advantages, drawbacks, approaches, practical details, and some points that should be considered in the experimental methods to reach reliable and promising conclusions are also discussed.