Chemical pretreatments mostly involve the use of acids and

bases in biomass hydrolysis [26]. Acid hydrolysis employs

concentrated and diluted H2SO4 or HCl to treat the lignocel-
lulosic biomass [19]. Dilute acid hydrolysis has replaced the
concentrated acid hydrolysis due to the fact that concentrated
acids are: (1) hazardous to handle and need reactors resistant to
corrosion, (2) required to be recovered after digestion to make
the process economically feasible and (3) less efficient in
achieving high reaction rates than dilute acids. Despite its
many advantages, dilute acid hydrolysis results in the forma-
tion of furfurals. Other undesirable components found in bio-
mass hydrolysates that are inhibitory to fermentation include
sugar degradation products (e.g. hydroxymethylfurfural or
HMF and levulinic acid), hemicellulose degradation products
(e.g. acetic acid, ferulic acid, glucuronic acid and p-coumaric
acid) and lignin breakdown products (e.g. syringaldehyde and
syringic acid). Irrespective of the pretreatment and hydrolysis
method used, it is often difficult to eliminate the chances for
generation of these inhibitory compounds.
Alkaline hydrolysis uses bases such as NH4OH and NaOH.
However, this pretreatment is expensive and the recovery and
recycling of bases from the system is often difficult [34, 35].
An advantage of using NH4OH is that the volatile nature of
NH 3 makes it effective in improving cellulose digestion.
Alkaline hydrolysis of lignocellulosic biomass depends on
its lignin content and overrules acid hydrolysis in degrading
lesser sugars with easy recovery of caustic salts. It causes
saponification of intermolecular ester bonds, cross-linking
xylan hemicellulose and other components.
The organosolv process has the direct action of water and
dissolved organic solvents such as ethanol, methanol and
acetone usually in combination with an acid to solubilize the
lignin and hydrolyze hemicellulose [36]. The process temper-
atures may vary from room temperature up to 180–200 °C
depending on the nature of organic solvent [42]. The major
drawback of this pretreatment is the production of furfurals
that may inhibit subsequent processes and result in low recov-
ery of pentose sugars. Furfural is a significant inhibitor of
ethanol production from hemicellulose hydrolysate and even
its low concentrations of 3–15 mM can adversely affect the
ethanol production rates [33]. The production of inhibitors is
found in both steam explosion and organosolv pretreatments.
The final concentrations of inhibitors in steam explosion can
be reduced by washing the exploded biomass with water [26].
This is quite difficult in case of organosolv process because of
the presence of organic solvents (e.g. ethanol, methanol and
acetone) in the hydrolysing medium [27]. There are additional
costs involved in solvent draining, evaporation and condensa-
tion to separate the aqueous and organic phases. Moreover,
ethanol acts as an inhibitor for the hydrolysis process as
suggested by Chiaramonti et al. [27]. However, organosolv
pretreatment is beneficial in higher cellulose digestibility and
recovery of hemicelluloses present in soft- and hardwood
from the water-soluble stream.

Recently, ionic liquids are gaining interest in biomass hy-

drolysis and being attractive alternatives to volatile and unsta-
ble organic solvents due to their high thermal stability and
nearly absolute nonvolatility. Ionic liquids are organic salts that
usually melt at temperatures less than 100 °C and are able to
dissolve polar and nonpolar organic, inorganic and polymeric
compounds. The ionic liquid, 1-ethyl-3-methylimidazolium
acetate, has found application in solubilizing cellulose and
reducing its crystallinity in switchgrass [43], and extracting
lignin from wood [44]. The reconstituted cellulose after ionic
liquid dissolution had lower degrees of crystallinity than native
cellulose which resulted in better accessibility of the polysac-
charide chains to cellulase