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.

Physicochemical characterization of particulate emissions from a compression ignition engine employing two injection technologies and three fuels

Alternative fuels and injection technologies are a necessary component of particulate emission reduction strategies for compression ignition engines. Consequently, this study undertakes a physicochemical characterization of diesel particulate matter (DPM) for engines equipped with alternative injection technologies (direct injection and common rail) and alternative fuels (ultra low sulfur diesel, a 20% biodiesel blend, and a synthetic diesel). Particle physical properties were addressed by measuring particle number size distributions, and particle chemical properties were addressed by measuring polycyclic aromatic hydrocarbons (PAHs) and reactive oxygen species (ROS). Particle volatility was determined by passing the polydisperse size distribution through a thermodenuder set to 300 °C. The results from this study, conducted over a four point test cycle, showed that both fuel type and injection technology have an impact on particle emissions, but injection technology was the more important factor. Significant particle number emission (54%–84%) reductions were achieved at half load operation (1% increase–43% decrease at full load) with the common rail injection system; however, the particles had a significantly higher PAH fraction (by a factor of 2 to 4) and ROS concentrations (by a factor of 6 to 16) both expressed on a test-cycle averaged basis. The results of this study have significant implications for the health effects of DPM emissions from both direct injection and common rail engines utilizing various alternative fuels.

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.

Design and construction of fixed bed pyrolysis system and plum seed pyrolysis for bio-oil production

This work investigated the production of bio oil from plum seed (Zyziphus jujuba) by fixed bed pyrolysis technology. A fixed bed pyrolysis system has been designed and fabricated for production of bio oil. The major components of the system are: fixed bed reactor, liquid condenser and liquid collector. Nitrogen gas was used to maintain the inert atmosphere in the reactor where the pyrolysis reaction takes place. The feedstock considered in this study is plum seed as it is available waste material in Bangladesh. The reactor is heated by means of a cylindrical biomass external heater. Rice husk was used as the energy source. The products are oil, char and gas. The parameters varied are reactor bed temperature, running time and feed particle size. The parameters are found to influence the product yields significantly. The maximum liquid yield of 39 wt% at 5200C for a feed particle size of 2.36-4.75 mm and a gas flow rate of 8 liter/min with a running time of 120 minute. The pyrolysis oil obtained at these optimum process conditions are analyzed for some of their properties as an alternative fuel. The density of the liquid was closer with diesel. The viscosity of the plum seed liquid was lower than that of the conventional fuels. The calorific value of the pyrolysis oil is one half of the diesel fuel.

Valorization of solid tire wastes available in Bangladesh by thermal treatment

In this study available solid tire wastes in Bangladesh were characterized through proximate and ultimate analyses, gross calorific values and thermogravimetric analysis to investigate their suitability as feedstock for thermal recycling by pyrolysis technology. A new approach in heating system, fixedbed fire-tube heating pyrolysis reactor has been designed and fabricated for the recovery of liquid hydrocarbons from solid tire wastes. The tire wastes were pyrolysed in the internally heated fixed-bed fire-tube heating reactor and maximum liquid yield of 46-55 wt% of solid tire waste was obtained at a temperature of 475 oC, feed size 4 cm3, with a residence time of 5 s under N2 atmosphere. The liquid products were characterized by physical properties, elemental analysis, FT-IR, 1H-NMR, GC MS techniques and distillation. The results show that the liquid products are comparable to petroleum fuels whereas fractional distillations and desulphurization are essential to be used as alternative for diesel engine fuels.

Production of liquid fuel and activated carbon from mahogany seed by using pyrolysis technology

The renovation of biomass waste in the form of Mahogany seed waste into bio-fuel as well as activated carbon by fixed bed pyrolysis reactor has been taken into consideration in this study. The mahogany seed in particle form is pyrolyzed in an enormously heated fixed bed reactor with nitrogen as the carrier gas. The reactor is heated from 4000C to 6000C using a external heater in which rice husk and charcoal are used as the heater biomass fuel. Reactor bed temperature, running time and feed particle size have been varied to get the optimum operating conditions of the system. The parameters are found to influence the product yields to a large extent. A maximum liquid and char yield are 49 wt. % and 35 wt. % respectively obtained at a reactor bed temperature 5000C when the running time is 90 minutes. Acquired pyrolyzed oil at these optimal process conditions were analyzed for some of their properties as an alternative fuel. The oil possesses comparable flame temperature, favorable flash point and reasonable viscosity along with somewhat higher density. The kinematic viscosity of the derived fuel is 3.8 cSt and density is 1525 kg/m3. The higher calorific value is found 32.4 MJ/kg which is significantly higher than other biomass derived fuel. Moderate adsorption capacity of the prepared activated carbon in case of methyl blue & tea water was also revealed.

An investigation of gaseous and particulate emissions from compression ignition engines operated with alternative fuels, injection technologies, and combustion strategies

Whilst the compression ignition (CI) engine exhibits many design advantages relative to its spark ignition engine counterpart; such as: high thermal efficiency, fuel economy and low carbon monoxide and hydrocarbon emissions, the issue of Diesel Particulate Matter (DPM) emissions continues to be an unresolved problem for the CI engine. Primarily, this thesis investigates a range of DPM mitigation strategies such as alternative fuels, injection technologies and combustion strategies conducted with a view to determine their impact on the physico-chemical properties of DPM emissions, and consequently to shed light on their likely human health impacts. Regulated gaseous emissions, Nitric oxide (NO), Carbon monoxide (CO), and Hydrocarbons (HCs), were measured in all experimental campaigns, although the major focus in this research program was on particulate emissions...

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.