High Conversion of Concentrated Sugars to 5-Hydroxymethylfurfural over a Metal-free Carbon Catalyst: Role of Glucose-Fructose Dimers.

To reduce the production cost of chemicals from renewable resources, the feedstock loading must be high and the catalyst must be of low cost and efficient. In this study, at a very short reaction time of 10 min at 125 °C, concentrated sugar solutions (20 wt %, 101 wt % on solvent) were converted to 5-hydroxymethylfurfural (HMF) over a cotton gin trash (CGT)-derived sulfonated carbon catalyst in a 1-butyl-3-methyl-imidazolium chloride ([BMIM]Cl) and 2-methyltetrahydrofuran (MeTHF) biphasic system. We report, for the first time, that the presence of glucose either as a covalently bonded monomer in sucrose or in a mixture with fructose achieved yields of HMF up to 62 mol % compared to a value of only 39 mol % obtained with fructose on its own. In the concentrated reaction medium, glucose, fructose, and sucrose molecules produce difructose anhydrides, dimers/reversion products, and sucrose isomers. The glucose-fructose dimers formed in sucrose and glucose/fructose reaction systems play a critical role in the transformation of the sugars to a higher-than-expected HMF yield. Thus, a strategy of using cellulosic glucose, where it is partially converted to fructose content and the high sugar concentration sugar mixture is then converted to HMF, should be exploited for future biorefineries.

Selective depolymerization of sugarcane bagasse anaerobic digestate to highly stable phenols-rich bio-oil with the iron-doped K-feldspar catalyst.

Sustainable implementation of thermochemical conversion of biomass to targeted products is dependent on innovations in catalyst design and tuning of structure-property relationships. This study details the use of potassium feldspar (K-feldspar) as a support doped with different iron (Fe) concentrations via wet impregnation (WI) method for hydrothermal liquefaction (HTL) of sugarcane bagasse anaerobic digestate. The Fe/K-feldspar supported catalysts were synthesized and characterized using X-ray diffraction, Inductively Coupled Plasma Optical Emission spectroscopy, Brunauer-Emmet-Teller and Scanning Electron Microscopy analytical methods. Amongst all the catalysts, K-feldspar dopped with 10 wt% Fe (WI-10) was more effective, producing 51.2 wt% bio-crude. The catalyst's activity has been related to the balanced proportion of the microcline: sanidine: haematite (2.8:3.3:1) phases of Fe present on the catalyst, the surface area (porosity), and the surface functionality, thus conferring desirable activity properties. In addition, the WI-10 catalyst had a better selectivity towards substituted phenols that can potentially be used for higher-value applications such as the production of Nylons 6 and 66, and bioplastics. The bio-oil produced with WI-10 has also been demonstrated to be highly stable. The catalyst was reusable up to four times maintaining moderate catalytic performance, and a simple regeneration protocol was shown to restore the activity of the catalyst. The resulting solid residue also exhibited promise as a viable material for use in electrodes for Lithium-ion batteries (LiB). Therefore, this research has demonstrated a promising and sustainable resource recovery strategy for valorising wet biomass wastes into streams of useful products for valuable chemical production and energy application.

Effective Adsorption of Colorants from Sugarcane Juice by Bagasse-Based Biochar-Hydroxyapatite Composite.

The clarification of sugarcane juice is a crucial stage in the sugar manufacturing process, as it affects evaporator performance, sugar quality and yield. The emergence of environmentally friendly and efficient adsorption technology has resulted in widespread interest in carbon-based materials. However, their low adsorption capacity and reusability make them unsuitable for processing sugarcane juice. Here, we provide a cost-effective and sustainable method to dope hydroxyapatite (HAP) nanoparticles on porous carbon (BBC) derived from sugarcane bagasse (BBC-HAP). The composite shows excellent adsorption capacity for color extract from sugarcane juice of 313.33 mg/g, far more effective than the commercially available carbon-based adsorbents. Isotherm studies show that the adsorption of BBC-HAP composite to the colorants is a monolayer process. The pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models demonstrate that the adsorption process is dominated by chemisorption and supplemented by physical adsorption.

Effects of pretreatment methods on biomethane production kinetics and microbial community by solid state anaerobic digestion of sugarcane trash.

Solid state anaerobic digestion (SS-AD) of lignocellulose is effective in improving biomethane productivity but is limited by low biomass digestibility and lack of substrate-specific working microorganisms. In this study, the effects of different pretreatment methods on biomethane production by SS-AD of sugarcane trash were studied. The biomethane production, fitted to a modified Gompertz's model, predicted a maximum methane yield of 214.2 L/kg volatile solids (VS) and productivity of 6.9 L/kg VS/day from KOH-pretreated trash, respectively. Microbial community analysis showed that bacterial community was significantly associated with volatile acids and pretreatment types while archaeal community was significantly associated with methane yield. Microbial community dynamics was revealed in SS-AD. Main genera related to pretreatment method were identified and discussed. This study generated important information on SS-AD of lignocellulosic biomass pretreated by different methods, which is useful for developing bioaugmentation strategies to improve biomethane production by SS-AD.

Closing the loop: Valorizing pyrolyzed waste tyre residue into functional carbon materials, SiO2 with exceptionally high silanol groups, and Zn salt.

This study aims to identify suitable processing conditions for converting pyrolytic solid residue from off-the-road tyres (OTR) to improve carbon materials properties that can be used in multiple applications and the recovery of minerals from OTR. Pyrolysis of OTR at 800 °C and a heating rate 2 °C.min-1 gave a carbon material with the highest surface area, most defective carbon structures, and the highest micro-porosity. This operating condition was used to compare the conventional three-step carbonization approach, which involves a demineralization stage that produces high volumes of toxic wastewater, with a two-step approach that bypasses this stage. Analysis of the carbon structures showed that the quality of the carbon material from the two-step approach is similar to the three-step approach. This two-step approach resulted in a solid and a liquid phase, in which âˆ¼ 93.4% of Zn was selectively fractionated to the liquid phase. The wastewater from the acid wash of the carbonized OTR was neutralized to recover the SiO2, of which 55.5% was reactive SiO2. The SiO2 was found to have an exceptionally high cross-linking ratio of 5.94, achievable only when SiO2 is reacted with silane groups. The study demonstrated that the engineered carbon material from OTR has a H2 uptake of 1.03 wt% at 77 K and 1.2 bar, and the sulfonated counterpart was an effective catalyst (64% conversion) for the Aldol condensation of levunilic acid to two dimer products [tetrahydro-2- methyl-5,γ-dioxo-2-furanpentanoic acid (TMDFA) and 3-(2-methyl-5-oxo- tetrahydrofuran-2-yl)-4-oxopentanoic acid (MOTOA)] that are precursors for fuels and chemicals.

Formation of Volatile and Aroma Compounds during the Dehydration of Membrane-Clarified Sugarcane Juice to Non-Centrifugal Sugar.

The development of volatile compounds and their precursors during the dehydration process of membrane-clarified sugarcane juice to non-centrifugal sugar (NCS) was investigated. Head-space solid phase microextraction/gas chromatography-mass spectrometry (HS-SPME/GC-MS) coupled with chemometrics was employed to assess the differences at the various stages of the dehydration process. A total of 111 volatile compounds were identified, among which 57 were endogenous compounds from sugarcane juice and displayed an attenuated abundance in the first 30 min. Typical oxygen and nitrogen heterocyclic compounds, including furans and pyrazines, and aldehydes derived were found to be the main volatiles contributing to the formation of NCS characteristic aroma, with phenols, alcohols, esters, acids, and sulfur compounds as supplementary odor. Free amino acids and reducing sugars were identified as important precursors for the aroma development process. The low temperature (90-108 °C) and micro vacuum condition (-0.03 MPa) approach used in this study could be an alternative option for the manufacture of NCS.

Environmentally friendly acetic acid/steam explosion/supercritical carbon dioxide system for the pre-treatment of wheat straw.

It is well established that pretreatment of lignocellulosic biomass is required to achieve an effective enzymatic saccharification process. At the present time, most of the touted pre-treatment technologies would cause environmental pollution and unsustainable water use for the pretreated material prior to enzymatic saccharification. To address these shortcomings, the pretreatment technology which combines the supercritical CO2, SC-CO2 (a green solvent), acetic acid, and steam explosion was used to assess the pretreatment of wheat straw for enzymatic saccharification. The effects of solvent concentration, impregnation temperature and time, pre-treatment time, and temperature, as well as SC-CO2 pressure, contact time, and temperature, were evaluated. The results identified that at the optimum SC-CO2 pressure of 18 MPa, the highest amount of reducing sugars (RS) was produced from the cellulosic pulp using Acetic acid/Steam/SC-CO2 at 200 °C for 30 min, a value 20% more than the pulp produced with the Water/Steam/SC-CO2. The effectiveness of the pretreatment process was attributed not only to delignification and defibrillation but also to the exposure of the cellulose structure evidenced from the proportion of the ß-glycosidic linkages as shown by FTIR. Passing SC-CO2 after the pretreatment reduces the amounts of fermentation inhibitors and eliminates the use of wash water.

A systematic evaluation of biomethane production from sugarcane trash pretreated by different methods.

Biomethane production was systematically evaluated with sugarcane trash pretreated by liquid hot water (LHW), dilute acid (DA) and KOH solutions. Multiple linear regression analysis identified glucan in pretreated solid residue as well as C5 sugars and acetic acid in pretreatment hydrolysate as the key parameters affecting biomethane potentials. Moreover, biomethane production was best simulated using Chen & Hashimoto model with a predicted highest methane yield of 187 mL/g initial total solids (TS) based on LHW (130 °C for 15 min) and KOH (10% on trash, 150 °C for 60 min) pretreatments. KOH pretreatment led to a biomethane yield of 167 mL/g initial TS at day 25, 82%, 34% and 33% higher than those achieved with untreated and pretreated trash samples with optimal LHW and DA conditions, respectively. This study led to the identification of best kinetic model and pretreatment condition for biomethane production from sugarcane trash through a systematic evaluation.

Heterogeneous Catalytic Conversion of Sugars Into 2,5-Furandicarboxylic Acid.

Achieving the goal of living in a sustainable and greener society, will need the chemical industry to move away from petroleum-based refineries to bio-refineries. This aim can be achieved by using biomass as the feedstock to produce platform chemicals. A platform chemical, 2,5-furandicarboxylic acid (FDCA) has gained much attention in recent years because of its chemical attributes as it can be used to produce green polymers such polyethylene 2,5-furandicarboxylate (PEF) that is an alternative to polyethylene terephthalate (PET) produced from fossil fuel. Typically, 5-(hydroxymethyl)furfural (HMF), an intermediate product of the acid dehydration of sugars, can be used as a precursor for the production of FDCA, and this transformation reaction has been extensively studied using both homogeneous and heterogeneous catalysts in different reaction media such as basic, neutral, and acidic media. In addition to the use of catalysts, conversion of HMF to FDCA occurs in the presence of oxidants such as air, O2, H2O2, and t-BuOOH. Among them, O2 has been the preferred oxidant due to its low cost and availability. However, due to the low stability of HMF and high processing cost to convert HMF to FDCA, researchers are studying the direct conversion of carbohydrates and biomass using both a single- and multi-phase approach for FDCA production. As there are issues arising from FDCA purification, much attention is now being paid to produce FDCA derivatives such as 2, 5-furandicarboxylic acid dimethyl ester (FDCDM) to circumvent these problems. Despite these technical barriers, what is pivotal to achieve in a cost-effective manner high yields of FDCA and derivatives, is the design of highly efficient, stable, and selective multi-functional catalysts. In this review, we summarize in detail the advances in the reaction chemistry, catalysts, and operating conditions for FDCA production from sugars and carbohydrates.

Effect of HCOOK/Ethanol on Fe/HUSY, Ni/HUSY, and Ni-Fe/HUSY Catalysts on Lignin Depolymerization to Benzyl Alcohols and Bioaromatics.

We have investigated the production of benzyl alcohols and bioaromatics via the reductive lignin depolymerization process over Fe/H-style ultrastable Y (HUSY), Ni/HUSY, and Ni-Fe/HUSY catalysts using HCOOK/ETOH in air. Synergy effect between HCOOK and the catalysts improved the depolymerization process, resulting in a higher bio-oil recovery. HCOOK does not act solely as an in situ hydrogen source; it also interacts with lignin to enable its initial depolymerization via a base-catalyzed mechanism to low-molecular-weight fragments, and in tandem with the catalyst, the hydrogenolysis rate of the depolymerized lignin monomers was enhanced. Fe/HUSY displayed an excellent activity for the catalytic reductive step in contrast to Ni/HUSY and Ni-Fe/HUSY by facilitating methoxy group removal via hydrogenolysis, thereby contributing to the yield and stabilization of the low-molecular-weight aromatics [diethyl ether (DEE)-soluble products]. Fe/HUSY gave the highest DEE product yield of >99 wt % and a total benzyl alcohol yield of 16 wt % with a total selectivity of 47 wt % (60 wt % for aromatic alcohols). Fe/HUSY was reused for the lignin depolymerization reaction without much loss of its initial activity, giving 13 wt % yield of benzyl alcohols with a selectivity of 58 wt % (77 wt % for aromatic alcohols).

Starch composites with aconitic acid.

The aim of this project is to examine the effectiveness of using aconitic acid (AcA), a tricarboxylic acid which contains a carbon/carbon double bond (CC), to enhance the properties of starch-based films. Starch/glycerol cast films were prepared with 0, 2, 5, 10 and 15wt% AcA (starch wt% basis) and the properties analysed. It was shown that AcA acted as both a cross-linking agent and also a strong plasticising agent. The 5wt% AcA derived starch films were the most effectively cross-linked having the lowest solubility (28wt%) and decreased swelling coefficient (35vol.%) by approximately 3 times and 2.4 times respectively compared to the control film submerged in water (23°C). There was also a significant increase in the film elongation at break by approximately 35 times (compared to the control) with the addition of 15wt% AcA, emphasising the plasticising effect of AcA. However, generally there was a reduced tensile strength, softening of the film, and reduced thermal stability with increased amounts of AcA.

Effects of glycerol on enzymatic hydrolysis and ethanol production using sugarcane bagasse pretreated by acidified glycerol solution.

In this study, for the first time the effects of glycerol on enzymatic hydrolysis and ethanol fermentation were investigated. Enzymatic hydrolysis was inhibited slightly with 2.0 wt% glycerol, leading to reduction in glucan digestibility from 84.9% without glycerol to 82.9% (72 h). With 5.0 wt% and 10.0 wt% glycerol, glucan digestibility was reduced by 4.5% and 11.0%, respectively. However, glycerol did not irreversibly inhibit cellulase enzymes. Ethanol fermentation was not affected by glycerol up to 5.0 wt%, but was inhibited slightly at 10.0 wt% glycerol, resulting in reduction in ethanol yield from 86.0% in the absence of glycerol to 83.7% (20 h). Based on the results of laboratory and pilot-scale experiments, it was estimated that 0.142 kg ethanol can be produced from 1.0 kg dry bagasse (a glucan content of 38.0%) after pretreatment with acidified glycerol solution.

A multi-criteria analysis approach for ranking and selection of microorganisms for the production of oils for biodiesel production.

Oleaginous microorganisms have potential to be used to produce oils as alternative feedstock for biodiesel production. Microalgae (Chlorella protothecoides and Chlorella zofingiensis), yeasts (Cryptococcus albidus and Rhodotorula mucilaginosa), and fungi (Aspergillus oryzae and Mucor plumbeus) were investigated for their ability to produce oil from glucose, xylose and glycerol. Multi-criteria analysis (MCA) using analytic hierarchy process (AHP) and preference ranking organization method for the enrichment of evaluations (PROMETHEE) with graphical analysis for interactive aid (GAIA), was used to rank and select the preferred microorganisms for oil production for biodiesel application. This was based on a number of criteria viz., oil concentration, content, production rate and yield, substrate consumption rate, fatty acids composition, biomass harvesting and nutrient costs. PROMETHEE selected A. oryzae, M. plumbeus and R. mucilaginosa as the most prospective species for oil production. However, further analysis by GAIA Webs identified A. oryzae and M. plumbeus as the best performing microorganisms.

Calcium phosphate flocs and the clarification of sugar cane juice from whole of crop harvesting.

Sugar cane biomass is one of the most viable feedstocks for the production of renewable fuels and chemicals. Therefore, processing the whole of crop (WC) (i.e., stalk and trash, instead of stalk only) will increase the amount of available biomass for this purpose. However, effective clarification of juice expressed from WC for raw sugar manufacture is a major challenge because of the amounts and types of non-sucrose impurities (e.g., polysaccharides, inorganics, proteins, etc.) present. Calcium phosphate flocs are important during sugar cane juice clarification because they are responsible for the removal of impurities. Therefore, to gain a better understanding of the role of calcium phosphate flocs during the juice clarification process, the effects of impurities on the physicochemical properties of calcium phosphate flocs were examined using small-angle laser light scattering technique, attenuated total reflectance Fourier transformed infrared spectroscopy, and X-ray powder diffraction. Results on synthetic sugar juice solutions showed that the presence of SiO2 and Na(+) ions affected floc size and floc structure. Starch and phosphate ions did not affect the floc structure; however, the former reduced the floc size, whereas the latter increased the floc size. The study revealed that high levels of Na(+) ions would negatively affect the clarification process the most, as they would reduce the amount of suspended particles trapped by the flocs. A complementary study on prepared WC juice using cold and cold/intermediate liming techniques was conducted. The study demonstrated that, in comparison to the one-stage (i.e., conventional) clarification process, a two-stage clarification process using cold liming removed more polysaccharides (≤19%), proteins (≤82%), phosphorus (≤53%), and SiO2 (≤23%) in WC juice but increased Ca(2+) (≤136%) and sulfur (≤200%).

Effects of mesostructured silica catalysts on the depolymerization of organosolv lignin fractionated from woody eucalyptus.

Isolated and purified organosolv eucalyptus wood lignin was depolymerized at different temperatures with and without mesostructured silica catalysts (i.e., SBA-15, MCM-41, ZrO2-SBA-15 and ZrO2-MCM-41). It was found that at 300°C for 1h with a solid/liquid ratio of 0.0175/1 (w/v), the SBA-15 catalyst with high acidity gave the highest syringol yield of 23.0% in a methanol/water mixture (50/50, wt/wt). Doping with ZrO2 over these catalysts did not increase syringol yield, but increased the total amount of solid residue. Gas chromatography-mass spectrometry (GC-MS) also identified other main phenolic compounds such as 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone, 1,2-benzenediol, and 4-hydroxy-3,5-dimethoxy-benzaldehyde. Analysis of the lignin residues with Fourier transform-infrared spectroscopy (FT-IR) indicated decreases in the absorption bands intensities of OH group, CO stretching of syringyl ring and aromatic CH deformation of syringol unit, and an increase in band intensities associated with the guaiacyl ring, confirming the type of products formed.

Degradation of hydroxycinnamic acid mixtures in aqueous sucrose solutions by the Fenton process.

The degradation efficiencies and behaviors of caffeic acid (CaA), p-coumaric acid (pCoA), and ferulic acid (FeA) in aqueous sucrose solutions containing the mixture of these hydroxycinnamic acids (HCAs) were studied by the Fenton oxidation process. Central composite design and multiresponse surface methodology were used to evaluate and optimize the interactive effects of process parameters. Four quadratic polynomial models were developed for the degradation of each individual acid in the mixture and the total HCAs degraded. Sucrose was the most influential parameter that significantly affected the total amount of HCA degraded. Under the conditions studied there was a <0.01% loss of sucrose in all reactions. The optimal values of the process parameters for a 200 mg/L HCA mixture in water (pH 4.73, 25.15 °C) and sucrose solution (13 mass %, pH 5.39, 35.98 °C) were 77% and 57%, respectively. Regression analysis showed goodness of fit between the experimental results and the predicted values. The degradation behavior of CaA differed from those of pCoA and FeA, where further CaA degradation is observed at increasing sucrose and decreasing solution pH. The differences (established using UV/vis and ATR-FTIR spectroscopy) were because, unlike the other acids, CaA formed a complex with Fe(III) or with Fe(III) hydrogen-bonded to sucrose and coprecipitated with lepidocrocite, an iron oxyhydroxide.

Glycerol carbonate as green solvent for pretreatment of sugarcane bagasse.

BACKGROUND: Pretreatment of lignocellulosic biomass is a prerequisite for effective saccharification to produce fermentable sugars. In this study, "green" solvent systems based on acidified mixtures of glycerol carbonate (GC) and glycerol were used to treat sugarcane bagasse and the roles of each solvent in deconstructing biomass were determined. RESULTS: Pretreatment of sugarcane bagasse at 90°C for only 30 min with acidified GC produced a solid residue having a glucan digestibility of 90% and a glucose yield of 80%, which were significantly higher than a glucan digestibility of 16% and a glucose yield of 15% obtained for bagasse pretreated with acidified ethylene carbonate (EC). Biomass compositional analyses showed that GC pretreatment removed more lignin than EC pretreatment (84% vs 54%). Scanning electron microscopy (SEM) showed that fluffy and size-reduced fibres were produced from GC pretreatment whereas EC pretreatment produced compact particles of reduced size. The maximal glucan digestibility and glucose yield of GC/glycerol systems were about 7% lower than those of EC/ethylene glycol (EG) systems. Replacing up to 50 wt% of GC with glycerol did not negatively affect glucan digestibility and glucose yield. The results from pretreatment of microcrystalline cellulose (MCC) showed that (1) pretreatment with acidified alkylene glycol (AG) alone increased enzymatic digestibility compared to pretreatments with acidified alkylene carbonate (AC) alone and acidified mixtures of AC and AG, (2) pretreatment with acidified GC alone slightly increased, but with acidified EC alone significantly decreased, enzymatic digestibility compared to untreated MCC, and (3) there was a good positive linear correlation of enzymatic digestibility of treated and untreated MCC samples with congo red (CR) adsorption capacity. CONCLUSIONS: Acidified GC alone was a more effective solvent for pretreatment of sugarcane bagasse than acidified EC alone. The higher glucose yield obtained with GC-pretreated bagasse is possibly due to the presence of one hydroxyl group in the GC molecular structure, resulting in more significant biomass delignification and defibrillation, though both solvent pretreatments reduced bagasse particles to a similar extent. The maximum glucan digestibility of GC/glycerol systems was less than that of EC/EG systems, which is likely attributed to glycerol being less effective than EG in biomass delignification and defibrillation. Acidified AC/AG solvent systems were more effective for pretreatment of lignin-containing biomass than MCC.

Effect of pretreatment on saccharification of sugarcane bagasse by complex and simple enzyme mixtures.

Saccharification of sugarcane bagasse pretreated at the pilot-scale with different processes (in combination with steam-explosion) was evaluated. Maximum glucan conversion with Celluclast 1.5L (15-25FPU/g glucan) was in the following order: glycerol/HCl>HCl>H2SO4>NaOH, with the glycerol system achieving ≈ 100% conversion. Surprisingly, the NaOH substrate achieved optimum saccharification with only 8 FPU/g glucan. Glucan conversions (3.6-6%) obtained with mixtures of endo-1,4-ß-glucanase (EG) and ß-glucosidase (ßG) for the NaOH substrate were 2-6 times that of acid substrates. However, glucan conversions (15-60%) obtained with mixtures of cellobiohydrolase (CBH I) and ßG on acidified glycerol substrate were 10-30% higher than those obtained for NaOH and acid substrates. The susceptibility of the substrates to enzymatic saccharification was explained by their physical and chemical attributes. Acidified glycerol pretreatment offers the opportunity to simplify the complexity of enzyme mixtures required for saccharification of lignocellulosics.

Laboratory and pilot scale pretreatment of sugarcane bagasse by acidified aqueous glycerol solutions.

Pretreatment of sugarcane bagasse with acidified aqueous glycerol solution was evaluated at both laboratory and pilot scales. Laboratory scale pretreatment (4.00 g dry mass in 40.00 g liquid) with glycerol solutions containing ≤ 20 wt.% water and 1.2 wt.% HCl at 130°C for 60 min resulted in biomass having glucan digestibilities of ≥ 88%. Comparable glucan enzymatic digestibility of 90% was achieved with bagasse pretreated at pilot scale (10 kg dry mass in 60 kg liquid) using a glycerol solution containing 0.4 wt.% HCl and 17 wt.% water at 130°C for 15 min. We attribute more efficient pretreatment at pilot scale (despite shorter reaction time and reduced acid content) to improved mixing and heat transfer in a horizontal reactor. Pretreatment of sugarcane bagasse with acid-catalysed glycerol solutions likely produces glycerol-glycosides, which together with hydrolysed lignin are potential substrates for the production of biopolymers.

Pretreatment of sugarcane bagasse by acid-catalysed process in aqueous ionic liquid solutions.

A biomass pretreatment process was developed using acidified ionic liquid (IL) solutions containing 10-30% water. Pretreatment of sugarcane bagasse at 130°C for 30 min by aqueous 1-butyl-3-methylimidazolium chloride (BMIMCl) solution containing 1.2% HCl resulted in a glucan digestibility of 94-100% after 72 h of enzymatic hydrolysis. HCl was found to be a more effective catalyst than H(2)SO(4) or FeCl(3). Increasing acid concentration (from 0.4% to 1.2%) and reaction temperature (from 90 to 130°C) increased glucan digestibility. The glucan digestibility of solid residue obtained with the acidified BMIMCl solution that was re-used for three times was >97%. The addition of water to ILs for pretreatment could significantly reduce IL solvent costs and allow for increased biomass loadings, making the pretreatment by ILs a more economic proposition.