The chemistry of acid catalyzed delignification of sugarcane bagasse in the ionic liquid trihexyl tetradecyl phosphonium chloride

This article reports on the cleavage of lignin ß-aryl ether bonds in sugarcane bagasse by the ionic liquid (IL) trihexyl tetradecyl phosphonium chloride [P66614] Cl, in the presence of catalytic amounts of mineral acid fca. 0.4%). The deligniflcation process of bagasse was studied over a range of temperatures (120°C to 150°C) by monitoring the production of ß-ketones (indicative of cleavage of ß-aryl ethers) using FTIR spectroscopy and by compositional analysis of the undissolved fractions. Maximum deligniflcation was obtained at 150°C, with 52% of lignin removed from the original lignin content of bagasse. No deligniflcation was observed in the absence of acid, which suggests that the reaction is acid catalyzed with the IL solubilizing the lignin fragments. The rate of deligniflcation was significantly higher at 150°C, suggesting that crossing the glass transition temperature of lignin effects greater freedom of rotation about the propanoid carbon-carbon bonds and leads to increased cleavage of ß-aryl ethers. An attempt has been made to propose a probable mechanism of deligniflcation of bagasse with the phosphonuim IL. © Taylor & Francis Group, LLC.

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 30min by aqueous 1-butyl-3-methylimidazolium chloride (BMIMCl) solution containing 1.2% HCl resulted in a glucan digestibility of 94-100% after 72h 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.

Comparative study on adsorption of two cationic dyes by milled sugarcane bagasse

Adsorptions of Rhodamine B (RhB) and Basic Blue 9 (BB9, also known as methylene blue) by sugarcane bagasse of different surface areas were compared in this study. There was a small gain in the amount of dye removed by increasing bagasse surface area from 0.57 m2/g to 1.81 m2/g. BB9 adsorption was less sensitive to surface area change than RhB adsorption. Adsorption capacity of 250 mg/L RhB on 1 g/L bagasse was 65.5 mg/g compared to a value of 30.7 mg/g obtained with BB9 under the same conditions. Increasing adsorption temperature (from 30 °C to 50 °C) while having no effect on RhB adsorption, slightly decreased BB9 adsorption by ~4%. The differences in adsorption performances between these dyes have been related to the molecular structure of the dyes and the surface chemistry of bagasse.

Impact of prescribed burning on urban air quality : a case study

For fuel management and/or ecological reasons prescribed burnings are conducted each year across Australia. Smoke from prescribed burnings could be the major source of air pollution in urban environment during the period of intensive prescribed burning. To investigate the impact of prescribed burning on air quality and the characteristics of prescribed burning particles, field measurements were conducted during the end period of a prescribed burning event in September 2011, Brisbane, Australia.

Ionic liquid pre-treatment and fractionation of sugarcane bagasse for the production of bioethanol

Pretretament is an essential and expensive processing step for the manufacturing of ethanol from lignocellulosic raw materials. Ionic liquids are a new class of solvents that have the potential to be used as pretreatment agents. The attractive characteristics of ionic liquid pretreatment of lignocellulosics such as thermal stability, dissolution properties, fractionation potential, cellulose decrystallisation capacity and saccharification impact are investigated in this thesis. Dissolution of bagasse with 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) at high temperatures (110 �‹C to 160 �‹C) is investigated as a pretreatment process. Material balances are reported and used along with enzymatic saccharification data to identify optimum pretreatment conditions (150 �‹C for 90 min). At these conditions, the dissolved and reprecipitated material is enriched in cellulose, has a low crystallinity and the cellulose component is efficiently hydrolysed (93 %, 3 h, 15 FPU). At pretreatment temperatures < 150 �‹C, the undissolved material has only slightly lower crystallinity than the starting. At pretreatment temperatures . 150 �‹C, the undissolved material has low crystallinity and when combined with the dissolved material has a saccharification rate and extent similar to completely dissolved material (100 %, 3h, 15 FPU). Complete dissolution is not necessary to maximize saccharification efficiency at temperatures . 150 �‹C. Fermentation of [C4mim]Cl-pretreated, enzyme-saccharified bagasse to ethanol is successfully conducted (85 % molar glucose-to-ethanol conversion efficiency). As compared to standard dilute acid pretreatment, the optimised [C4mim]Cl pretreatment achieves substantially higher ethanol yields (79 % cf. 52 %) in less than half the processing time (pretreatment, saccharification, fermentation). Fractionation of bagasse partially dissolved in [C4mim]Cl to a polysaccharide rich and a lignin rich fraction is attempted using aqueous biphasic systems (ABSs) and single phase systems with preferential precipitation. ABSs of ILs and concentrated aqueous inorganic salt solutions are achievable (e.g. [C4mim]Cl with 200 g L-1 NaOH), albeit they exhibit a number of technical problems including phase convergence (which increases with increasing biomass loading) and deprotonation of imidazolium ILs (5 % - 8 % mol). Single phase fractionation systems comprising lignin solvents / cellulose antisolvents, viz. NaOH (2M) and acetone in water (1:1, volume basis), afford solids with, respectively, 40 % mass and 29 % mass less lignin than water precipitated solids. However, this delignification imparts little increase in saccharification rates and extents of these solids. An alternative single phase fractionation system is achieved simply by using water as an antisolvent. Regulating the water : IL ratio results in a solution that precipitates cellulose and maintains lignin in solution (0.5 water : IL mass ratio) in both [C4mim]Cl and 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc)). This water based fractionation is applied in three IL pretreatments on bagasse ([C4mim]Cl, 1-ethyl-3-methyl imidazolium chloride ([C2mim]Cl) and [C2mim]OAc). Lignin removal of 10 %, 50 % and 60 % mass respectively is achieved although only 0.3 %, 1.5 % and 11.7 % is recoverable even after ample water addition (3.5 water : IL mass ratio) and acidification (pH . 1). In addition the recovered lignin fraction contains 70 % mass hemicelluloses. The delignified, cellulose-rich bagasse recovered from these three ILs is exposed to enzyme saccharification. The saccharification (24 h, 15 FPU) of the cellulose mass in starting bagasse, achieved by these pretreatments rank as: [C2mim]OAc (83 %)>>[C2mim]Cl (53 %)=[C4mim]Cl(53%). Mass balance determinations accounted for 97 % of starting bagasse mass for the [C4mim]Cl pretreatment , 81 % for [C2mim]Cl and 79 %for [C2mim]OAc. For all three IL treatments, the remaining bagasse mass (not accounted for by mass balance determinations) is mainly (more than half) lignin that is not recoverable from the liquid fraction. After pretreatment, 100 % mass of both ions of all three ILs were recovered in the liquid fraction. Compositional characteristics of [C2mim]OAc treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are opposite to those of chloride IL treated solids. The former biomass characteristics resemble those imparted by aqueous alkali pretreatment while the latter resemble those of aqueous acid pretreatments. The 100 % mass recovery of cellulose in [C2mim]OAc as opposed to 53 % mass recovery in [C2mim]Cl further demonstrates this since the cellulose glycosidic bonds are protected under alkali conditions. The alkyl chain length decrease in the imidazolium cation of these ILs imparts higher rates of dissolution and losses, and increases the severity of the treatment without changing the chemistry involved.

Characterisation of sugarcane juice particles that influence the clarification process

Problems associated with processing whole sugarcane crop can be minimised by removing impurities during the clarification stage. As a first step, it is important to understand the colloidal chemistry of juice particles on a molecular level to assist development of strategies for effective clarification performance. This paper presents the composition and surface characteristics of colloidal particles originating from various juice types by using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), X-ray photoelectron spectroscopy(XPS) and zeta potential measurements. The composition and surface characteristics of colloidal juice particles are reported. The results indicate that there are three types of colloidal particles present, viz. an aluminosilicatecompound, silica and iron oxide, with the latter two being abundant. Proteins, polysaccharides and organic acids were identified on the surface of particles in juice. The overall particle charge varies from -2 mV to -6 mV. In comparison to juice expressed from burnt cane, the zeta potential values were more negative with juice particles originating from whole crop. This in part explains why these juices are difficult to clarify.

The potential for ethanol production from sugarcane in Australia

The Australian sugar industry processes approximately 35 million tonnes of sugarcane per year from 400 000 hectares of land. Sugar remains the principal revenue stream from sugarcane in Australia with less than 60 ML/y of fuel ethanol produced from final molasses at present. Modelling has been undertaken to estimate the potential ethanol production from the Australian sugar industry for integrated facilities producing both sugar and ethanol from the entire sugarcane resource. Although research aimed at developing commercial processes is ongoing, the use of a proportion of the bagasse and trash for ethanol production, in addition to juice and molasses fermentation, would allow significant increases in the scale of ethanol production from sugarcane in Australia, increasing total industry revenues while maintaining energy self sufficiency.

Combustion products of bulk aluminum rods burning in high pressure oxygen

Characterization of the combustion products released during the burning of commonly used engineering metallic materials may aid in material selection and risk assessment for the design of oxygen systems. The characterization of combustion products in regards to size distribution and morphology gives useful information for systems addressing fire detection. Aluminum rods (3.2-mm diameter cylinders) were vertically mounted inside a combustion chamber and ignited in pressurized oxygen by resistively heating an aluminum/palladium igniter wire attached to the bottom of the test sample. This paper describes the experimental work conducted to establish the particle size distribution and morphology of the resultant combustion products collected after the burning was completed and subsequently analyzed. In general, the combustion products consisted of a re-solidified oxidized slag and many small hollow spheres of size ranging from about 500 nm to 1000 µm in diameter, surfaced with quenched dendritic and grain-like structures. The combustion products were characterized using optical and scanning electron microscopy.

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.

Effects of pH on pretreatment of sugarcane bagasse using aqueous imidazolium ionic liquids

Pretreatments of sugarcane bagasse for saccharification using different acid-catalysed imidazolium IL solutions (containing 20% water) at 130 °C for 30 min were investigated. At the same solution pH, pretreatment effectiveness in terms of glucan digestibility, delignification and xylan removal were similar for aqueous 1-butyl-3-methylimidazolium methane sulfonate (BMIMCH3SO3), 1-butyl-3-methylimidazolium methyl sulfate (BMIMCH3SO4), 1-ethyl-3-methylimidazolium chloride (EMIMCl) and 1-butyl-3-methylimidazolium chloride (BMIMCl). Decreasing solution pH of aqueous IL systems from 6.0 to 0.4 increased bagasse delignification and xylan removal, and as a result, improved glucan digestibility. The glucan digestibilities for bagasse samples pretreated by IL solutions with pH ≤ 0.9 were > 90% after 72 h of enzymatic hydrolysis. Without pH adjustment, the effectiveness of these aqueous IL solutions (except BMIMCH3SO3 because of its low natural pH of 0.9) to deconstruct the biomass was poor and the glucan digestibilities of pretreated bagasse samples were < 20%. These results show that pretreatment effectiveness of aqueous imidazolium ILs can simply be estimated from solution pH rather than hydrogen bond basicity (β) of the IL solution.