Fuel Properties of Torrefied Biomass from Sapindus Pericarp Extraction Residue under a Wide Range of Pyrolysis Conditions

In this work, a novel biomass, the extraction residue of Sapindus pericarp (SP), was torrefied by using an electronic oven under a wide range of temperature (i.e., 200–320 °C) and residence times (i.e., 0–60 min). From the results of the thermogravimetric analysis (TGA) of SP, a significant weight loss was observed in the temperature range of 200–400 °C, which can be divided into the decompositions of hemicellulose (major)/lignin (minor) (200–320 °C) and cellulose (major)/lignin (minor) (320–400 °C). Based on the fuel properties of the feedstock SP and SP-torrefied products, the optimal torrefaction conditions can be found at around 280 °C for holding 30 min, showing that the calorific value, enhancement factor and energy yield of the torrefied biomass were enhanced to be 28.60 MJ/kg, 1.36 and 82.04 wt%, respectively. Consistently, the values of the calorific value, carbon content and molar carbon/hydrogen (C/H) ratio indicated an increasing trend at higher torrefaction temperatures and/or longer residence times. The findings showed that some SP-torrefied solids can be grouped into the characteristics of a lignite-like biomass by a van Krevelen diagram for all the SP-torrefied products. However, the SP-torrefied fuels would be particularly susceptible to the problems of slagging and fouling because of the relatively high contents of potassium (K) and calcium (Ca) based on the analytical results of the energy dispersive X-ray spectroscopy (EDS).

Geochemical investigation of hydrocarbon generation potential of coal from Raniganj Basin, India

Methane content in a coal seam is a necessary parameter for evaluating coal bed gas, and it poses an environmental risk to underground coal mining activities. Keeping in pace with comprehensive studies of coal bed gas, 12 coal samples were selected from the Sitarampur block of Raniganj Coalfield for analysis. The Petrographic examination illustrated that significant values of reactive macerals present in samples demonstrate that organic matter is dominated by the prominent source of aromatic hydrocarbons with a minor proportion of aliphatic hydrocarbon, which falls in the region of (Type III) kerogen, confirms the suitability for the potential of hydrocarbon generation. “A” factor (aliphatic/aromatic bands) and “C” factor (carbonyl/carboxyl bands) value concluded that the sample has the lowest aromaticity and the highest hydrocarbon-generating potential, which was also validated by the Van Krevelen diagram. The Van Krevelen diagram plots between the H/C and O/C ratio indicate that coal samples lie in the type III kerogen, and bituminous coal (gas prone zone) is present in the block, which is confirmed by the cross-plot between desorbed and total gas (cc/g). The in situ gas content values are high enough to produce methane from coal beds. The overall study concludes that the Sitarampur block from Raniganj Coalfield is suitable for hydrocarbon generation and extraction.

Upgrading fuel potentials of waste biomass via hydrothermal carbonization

In recent decades, massive exploitation of fossil fuels caused a growing demand for the production of energies from renewable sources. Hydrochar obtained from waste biomass via hydrothermal carbonization (HTC) possesses good potentials as a biofuel. Therefore, we performed HTC of corn cob, paulownia leaves, and olive pomace at different temperatures (180, 220, and 260 oC). The main goal of this study was to comparatively evaluate the influence of HTC conditions on the structure and fuel characteristics of the obtained solids. The results showed that the yields of hydrochar decrease significantly with increasing temperature in all samples. The carbon content and higher heating value increased and reached the highest values in hydrochars obtained at 260 oC, while the content of volatile matter decreased. Furthermore, the Van Krevelen diagram reveals that the transformation of feedstock to lignite-like products upon HTC was achieved. In this study, the results showed that processes of dehydration and decarboxylation during HTC provoke intensive biomass transformation and that hydrochars obtained at higher temperatures have significantly enhanced fuel properties and fewer volatiles compared to the feedstock.

Estimation of the characteristics with hydrothermal carbonisation temperature on poultry slaughterhouse wastes

This study is an assessment of the hydrothermal carbonisation of poultry slaughterhouse wastes sludge for the solid recovered fuel. The effects of hydrothermal carbonisation were evaluated by varying the reaction temperatures in the range of 170 °C–220 °C. After hydrothermal carbonisation was completed, the capillary suction time, time to filter, and particle size decreased by ranges of 170.4 to 25.9 s, 40 to 7.0 s, and 220 to 98 um, respectively, with increasing hydrothermal carbonisation temperature. This effect improved the dewaterability to release additional free water from the sludge. Moreover, hydrothermal carbonisation increased the heating value though the reduction of the hydrogen and oxygen content of solid fuel in addition to investigating drying performance. As shown in the Van Krevelen diagram, the H/C and O/C ratios decreased, in correlation with primary reactions of coalification. These results suggest that the hydrothermal carbonisation process is an advantageous technology in improving the properties of poultry slaughterhouse wastes as an alternative solid recovered fuel by converting the physical and chemical structure of the poultry slaughterhouse wastes in addition to also providing other benefits to treat organic and biomass waste.

Analysis of secondary organic aerosol formation and aging using positive matrix factorization of high-resolution aerosol mass spectra: application to the dodecane low-NO_x system

Positive matrix factorization (PMF) of high-resolution laboratory chamber aerosol mass spectra is applied for the first time, the results of which are consistent with molecular level MOVI-HRToF-CIMS aerosol-phase and CIMS gas-phase measurements. Secondary organic aerosol was generated by photooxidation of dodecane under low-NOx conditions in the Caltech environmental chamber. The PMF results exhibit three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition. The slope of the measured high-resolution aerosol mass spectrometer (HR-ToF-AMS) composition data on a Van Krevelen diagram is consistent with that of other low-NOx alkane systems in the same O : C range. Elemental analysis of the PMF factor mass spectral profiles elucidates the combinations of functionality that contribute to the slope on the Van Krevelen diagram.

Analysis of secondary organic aerosol formation and aging using positive matrix factorization of high-resolution aerosol mass spectra: application to the dodecane low-NO_x system

Positive matrix factorization (PMF) of high-resolution laboratory aerosol mass spectra is applied for the first time, the results of which are consistent with molecular level MOVI-HRToF-CIMS aerosol-phase and CIMS gas-phase measurements. Secondary organic aerosol was generated by photooxidation of dodecane under low-NOx conditions in the Caltech environmental chamber. The PMF results exhibit three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition. The slope of the measured high-resolution aerosol mass spectrometer (HR-ToF-AMS) composition data on a Van Krevelen diagram is consistent with that of other low-NOx alkane systems in the same O:C range. Elemental analysis of the PMF factor mass spectral profiles elucidates the combinations of functionality that contribute to the slope on the Van Krevelen diagram.

Elemental composition and oxidation of chamber organic aerosol

Recently, graphical representations of aerosol mass spectrometer (AMS) spectra and elemental composition have been developed to explain the oxidative and aging processes of secondary organic aerosol (SOA). It has been shown previously that oxygenated organic aerosol (OOA) components from ambient and laboratory data fall within a triangular region in the f44 vs. f43 space, where f44 and f43 are the ratios of the organic signal at m/z 44 and 43 to the total organic signal in AMS spectra, respectively; we refer to this graphical representation as the "triangle plot." Alternatively, the Van Krevelen diagram has been used to describe the evolution of functional groups in SOA. In this study we investigate the variability of SOA formed in chamber experiments from twelve different precursors in both "triangle plot" and Van Krevelen domains. Spectral and elemental data from the high-resolution Aerodyne aerosol mass spectrometer are compared to offline species identification analysis and FTIR filter analysis to better understand the changes in functional and elemental composition inherent in SOA formation and aging. We find that SOA formed under high- and low-NOx conditions occupy similar areas in the "triangle plot" and Van Krevelen diagram and that SOA generated from already oxidized precursors allows for the exploration of areas higher on the "triangle plot" not easily accessible with non-oxidized precursors. As SOA ages, it migrates toward the top of the triangle along a path largely dependent on the precursor identity, which suggests increasing organic acid content and decreasing mass spectral variability. The most oxidized SOA come from the photooxidation of methoxyphenol precursors which yielded SOA O/C ratios near unity. α-pinene ozonolysis and naphthalene photooxidation SOA systems have had the highest degree of mass closure in previous chemical characterization studies and also show the best agreement between AMS elemental composition measurements and elemental composition of identified species within the uncertainty of the AMS elemental analysis. In general, compared to their respective unsaturated SOA precursors, the elemental composition of chamber SOA follows a slope shallower than −1 on the Van Krevelen diagram, which is indicative of oxidation of the precursor without substantial losss of hydrogen, likely due to the unsaturated nature of the precursors. From the spectra of SOA studied here, we are able to reproduce the triangular region originally constructed with ambient OOA compents with chamber aerosol showing that SOA becomes more chemically similar as it ages. Ambient data in the middle of the triangle represent the ensemble average of many different SOA precursors, ages, and oxidative processes.

Changes in organic aerosol composition with aging inferred from aerosol mass spectra

Organic aerosols (OA) can be separated with factor analysis of aerosol mass spectrometer (AMS) data into hydrocarbon-like OA (HOA) and oxygenated OA (OOA). We develop a new method to parameterize H:C of OOA in terms of f43 (ratio of m/z 43, mostly C2H3O+, to total signal in the component mass spectrum). Such parameterization allows for the transformation of large database of ambient OOA components from the f44 (mostly CO2+, likely from acid groups) vs. f43 space ("triangle plot") (Ng et al., 2010) into the Van Krevelen diagram (H:C vs. O:C) (Van Krevelen, 1950). Heald et al. (2010) examined the evolution of total OA in the Van Krevelen diagram. In this work total OA is deconvolved into components that correspond to primary (HOA and others) and secondary (OOA) organic aerosols. By deconvolving total OA into different components, we remove physical mixing effects between secondary and primary aerosols which allows for examination of the evolution of OOA components alone in the Van Krevelen space. This provides a unique means of following ambient secondary OA evolution that is analogous to and can be compared with trends observed in chamber studies of secondary organic aerosol formation. The triangle plot in Ng et al. (2010) indicates that f44 of OOA components increases with photochemical age, suggesting the importance of acid formation in OOA evolution. Once they are transformed with the new parameterization, the triangle plot of the OOA components from all sites occupy an area in Van Krevelen space which follows a ΔH:C/ΔO:C slope of ~ −0.5. This slope suggests that ambient OOA aging results in net changes in chemical composition that are equivalent to the addition of both acid and alcohol/peroxide functional groups without fragmentation (i.e. C-C bond breakage), and/or the addition of acid groups with fragmentation. These results provide a framework for linking the bulk aerosol chemical composition evolution to molecular-level studies.