Sushil Adhikari

Catalytic pyrolysis of green algae for hydrocarbon production using H+ZSM-5 catalyst.

Microalgae are considered as an intriguing candidate for biofuel production due to their high biomass yield. Studies on bio-oil production through fast pyrolysis and upgrading to hydrocarbon fuels using algal biomass are limited as compared to other terrestrial biomass. Therefore, in this study, a fresh water green alga, Chlorella vulgaris, was taken for pyrolysis study. The average activation energy for pyrolysis zone was found to be 109.1 kJ/mol. Fixed-bed pyrolysis of algae gave a bio-oil yield of 52.7 wt.%, which accounts for 60.7 wt.% carbon yield. In addition, analytical pyrolysis of C. vulgaris was carried out in a Py/GC-MS to identify major compounds present in bio-oil with and without catalyst (H(+)ZSM-5). The study found that in catalytic-pyrolysis, as the catalyst loading increased from zero to nine times of the biomass, the carbon yield of aromatic hydrocarbons increased from 0.9 to 25.8 wt.%.

Physiochemical properties of bio-oil produced at various temperatures from pine wood using an auger reactor.

A fast pyrolysis process produces a high yield of liquid (a.k.a. bio-oil) and has gained a lot of interest among various stakeholders. Nonetheless, some of the properties inherent by the bio-oil create significant challenges for its wider applications. Quality of the bio-oil and its yield are highly dependent on process parameters, such as temperature, feedstock, moisture content and residence time. In this study, the effect of temperature on bio-oil quality and its yield were examined using pine wood, an abundant biomass source in the southeastern part of the United States. Physical properties of bio-oil such as pH, water content, higher heating value, solid content and ash were analyzed and compared with a recently published ASTM standard. Bio-oil produced from pine wood using an auger reactor met specifications suggested by the ASTM standard. Thirty-two chemical compounds were analyzed. The study found that the concentration of phenol and its derivatives increased with the increase in pyrolysis temperature whereas the concentration of guaiacol and its derivatives decreased as the temperature increased. Concentration of acetic and other acids remained almost constant or increased with the increase in temperature although the pH value of the bio-oil decreased with the increase in temperature.

Production of hydrocarbon fuels from biomass using catalytic pyrolysis under helium and hydrogen environments

This study is focused on hydrocarbon production through changing carrier gas and using zeolite catalysts during pyrolysis. A large reduction in high molecular weight, oxygenated compounds was noticed when the carrier gas was changed from helium to hydrogen during pyrolysis. A catalytic pyrolysis was conducted using two different methods based on how the biomass and catalysts were contacted together. For both methods, there was no significant change in the carbon yield with the change in pyrolysis environment. However, the mixing-method produced higher aromatic hydrocarbons than the bed-method. In addition, two methods were also tested using two ratios of biomass to catalyst. Nonetheless, there was no significant increase in hydrocarbon yield as the catalyst loading was increased from two to five times of biomass in the catalyst-bed method. In contrast to this, a significant increase was noticed for the catalytic-mixing method when the biomass to catalyst loading was increased from 1:4 to 1:9.

Effect of torrefaction on biomass structure and hydrocarbon production from fast pyrolysis

Torrefaction has been shown to improve the chemical composition of bio-oils produced from fast pyrolysis by lowering its oxygen content and enhancing the aromatic yield. A Py-GC/MS study was employed to investigate the effect of torrefaction temperatures (225, 250 and 275 °C) and residence times (15, 30 and 45 min) on product distribution from non-catalytic and H+ZSM-5 catalyzed pyrolysis of pinewood. During torrefaction, structural transformations in biomass constitutive polymers: hemicellulose, cellulose and lignin took place, which were evaluated using component analysis, solid state CP/MAS 13C NMR and XRD techniques. Torrefaction caused deacetylation and decomposition of hemicellulose, cleavage of aryl ether linkages and demethoxylation of lignin, degradation of cellulose and an overall increase in aromaticity of biomass, all of which affected the product yield from pyrolysis of torrefied biomass. For non-catalytic pyrolysis, selectivity of phenolic compounds increased with an increase in torrefaction severity while that of furan compounds decreased. In the case of catalytic pyrolysis, the sample torrefied at 225 °C-30 min and 250 °C-15 min resulted in a significant increase in aromatic hydrocarbon (HC) and also total carbon yield (approx. 1.6 times higher) as compared to catalytic pyrolysis of non-torrefied pine. Cleavage of aryl ether linkages and demethoxylation in lignin due to torrefaction caused increased yield of phenolic compounds, which in the presence of a catalyst were dehydrated to form aromatic HC.

Modeling for proximate analysis and heating value of torrefied biomass with vibration spectroscopy.

The goal of this study was to characterize the changes in biomass with torrefaction for near infrared reflectance (NIR) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy for sweetgum, loblolly pine, and switchgrass. Calibration models were built for the prediction of proximate analysis after torrefaction. Two dimensional (2D) correlation spectroscopy between NIR and FTIR was found to precisely explain the depolymerization at key functional groups located within hemicellulose, cellulose, and lignin. This novel 2D technique also demonstrated the possibility of assigning key NIR wavenumbers based on mid IR spectra. Hemicellulose based wavenumbers were found to be most sensitive to torrefaction severity with complete degradation at 250-275°C. Lignin associated wavenumbers exhibited the least degradation to severity but was still detected with 2D correlation spectroscopy. Finally, calibration models for proximate analysis were performed and while both systems could be used for rapid monitoring, NIR performed better than FTIR.

A comparison of three pH control methods for revealing effects of undissociated butyric acid on specific butanol production rate in batch fermentation of Clostridium acetobutylicum

AbstractpH control has been essential for butanol production with Clostridium acetobutylicum. However, it is not very clear at what pH level the acid crash will occur, at what pH level butanol production will be dominant, and at what pH level butyric acid production will be prevailing. Furthermore, contradictory results have been reported about required acidic conditions for initiation of solventogenesis. In this study, with the aim of further understanding the role of undissociated butyric acid in butanol production, we investigated the correlation between undissociated butyric acid concentration and specific butanol production rate in batch fermentation of Clostridium acetobutylicum by comparing three pH control approaches: NaOH neutralization (at 12, 24 or 36 h), CaCO3 supplementation (2, 5, or 8 g/l) and NaOAc buffering (pH 4.6, 5.0 or 5.6). By neutralizing the fermentation pH to ~5.0 at different time, we observed that neutralization should take place at the beginning of exponential phase (12 h), and otherwise resulting in lower concentrations of undissociated butyric acid, cell biomass and final butanol. CaCO3 supplementation extended cell growth to 36 h and resulted in higher butyrate yield under 8 g/L of CaCO3. In the NaOAc buffering, the highest specific butanol rate (0.58 h−1) was associated with the highest undissociated butyric acid (1.92 g/L). The linear correlation of the undissociated butyric acid with the specific butanol production rates suggested the undissociated butyric acid could be the major driving force for butanol production.

Distinct roles of residual xylan and lignin in limiting enzymatic hydrolysis of organosolv pretreated loblolly pine and sweetgum.

The interactions between xylan/lignin and cellulase enzymes play a key role in the effective hydrolysis of lignocellulosic biomass. Organosolv pretreated loblolly pine (OPLP) and sweetgum (OPSG) were used to quantitatively elucidate the distinct roles of residual xylan and lignin on enzymatic hydrolysis, based on the initial hydrolysis rates and the final hydrolysis yields. The initial hydrolysis rates of OPLP and OPSG were 1.45 (glucose) and 1.19 g/L/h (glucose), respectively, under the enzyme loading of 20 FPU/g glucan. The final glucan hydrolysis yields of OPLP and OPSG at 72 h were 76.4 and 98.9%, respectively. By correlating the amount of residual lignin and xylan to the initial hydrolysis rate and the final hydrolysis yield in OPLP and OPSG, a more accurate fundamental understanding of the roles of xylan and lignin in limiting the enzymatic hydrolysis has been developed. The higher amount of residual xylan (9.7%) in OPSG resulted in lower initial hydrolysis rate (1.19 g/L/h). The higher amount of residual lignin in OPLP (18.6%) resulted in lower final hydrolysis yield of glucan (76.4%). In addition, we observed in the simultaneous saccharification and fermentation (SSF) that ethyl xyloside was produced by the enzymatic catalysis of xylose/xylan and ethanol.

Environmental application of biochar: Current status and perspectives

In recent years, there has been a significant interest on biochar for various environmental applications, e.g., pollutants removal, carbon sequestration, and soil amelioration. Biochar has several unique properties, which makes it an efficient, cost-effective and environmentally-friendly material for diverse contaminants removal. The variability in physicochemical properties (e.g., surface area, microporosity, and pH) provides an avenue for biochar to maximize its efficacy to targeted applications. This review aims to highlight the vital role of surface architecture of biochar in different environmental applications. Particularly, it provides a critical review of current research updates related to the pollutants interaction with surface functional groups of biochars and the effect of the parameters variability on biochar attributes pertinent to specific pollutants removal, involved mechanisms, and competence for these removals. Moreover, future research directions of biochar research are also discussed.

Adsorption of glycerol from biodiesel washwaters.

The removal of glycerol by adsorption from biodiesel washwaters has been studied at room temperature using various adsorbent materials, including activated carbons, clay minerals, and natural and synthetic zeolites. Activated carbon exhibited the best adsorption for glycerol among the examined materials. Glycerol adsorption isotherms are obtained on activated carbons after treatment under different conditions. The Langmuir isotherm coefficients and the first‐order desorption kinetic parameters for glycerol on a coconut activated carbon were determined by fitting the experimental data. The adsorption of glycerol was increased by removing the functional groups from the carbon surface at high temperatures under N2 atmosphere, and was decreased by increasing surface functional groups through HNO3 oxidation. Compared with water, glycerol tends to adsorb more favourably on a hydrophobic carbon surface than on a hydrophilic one.

Improvement in HPLC separation of acetic acid and levulinic acid in the profiling of biomass hydrolysate.

5-Hydroxymethylfurfural (HMF) and furfural could be separated by the Aminex HPX-87H column chromatography, however, the separation and quantification of acetic acid and levulinic acid in biomass hydrolysate have been difficult with this method. In present study, the HPLC separation of acetic acid and levulinic acid on Aminex HPX-87H column has been investigated by varying column temperature, flow rate, and sulfuric acid content in the mobile phase. The column temperature was found critical in resolving acetic acid and levulinic acid. The resolution for two acids increased dramatically from 0.42 to 1.86 when the column temperature was lowered from 60 to 30 °C. So did the capacity factors for levulinic acid that was increased from 1.20 to 1.44 as the column temperature dropped. The optimum column temperature for the separation was found at 45 °C. Variation in flow rate and sulfuric acid concentration improved not as much as the column temperature did.