skip to main content


Title: Determination of size and porosity of chars during combustion of biomass particles
This research focused on the size and overall porosity (pore volume) of carbonaceous chars, originating from high-heating rates and high-temperature pyrolysis and/or combustion of biomass. Emphasis was given to torrefied biomass chars. First, the porosity of char residues of single biomass particles of known mass was determined, based on an assumed value of skeletal density and by comparing experimentally observed temperature-time histories with numerical predictions of their burnout times. The average char porosities (effective porosities) of several raw and torrefied biomass particles were calculated to be in the range of 92–95%. Thereafter, these deduced porosity values were input again to the model to calculate the size of chars of other biomass particle precursors, whose initial size and mass were not known. Such biomass particles were sieve-classified to different nominal size ranges. This time, besides the porosity, representative time-temperature profiles of biomass particles in the aforementioned size ranges were also input to the model. Biomass particles are highly irregular with large aspect ratios and, in many cases, they melt and spherodize under high heating rates and elevated temperatures. Knowledge of the initial size of the chars, upon extinction of the volatile flames, is needed for modeling their heterogeneous combustion phase. For this purpose, numerical predictions were in general agreement with measurements of char size obtained from both scanning electron microscopy of captured chars and real-time high-speed, high- magnification cinematographic observations of their combustion. Results showed that the generated chars of the examined biomass types were highly porous with large cavities. The average initial dimension of the chars, upon rapid pyrolysis, was in the range of 50–60% the mid-value of the mesh size of the sieves used to size-classify their highly irregular parent biomass particles.  more » « less
Award ID(s):
1810961
NSF-PAR ID:
10336356
Author(s) / Creator(s):
; ; ;
Editor(s):
Egolfopoulos, Fokion
Date Published:
Journal Name:
Combustion and flame
Volume:
242
ISSN:
0010-2180
Page Range / eLocation ID:
112182
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Abstract. There are many fuels used for domestic purposes in east Africa, producing a significant atmospheric burden of the resulting aerosols, which includes biomass burning particles. However, the aerosol physicochemical properties are poorly understood. Here, the combustion of eucalyptus, acacia, and olive fuels was performed at 500 and 800 ∘C in a tube furnace, followed by immediate filter collection for fresh samples or introduction into a photochemical chamber to simulate atmospheric photochemical aging under the influence of anthropogenic emissions. The aerosol generated in the latter experiment was collected onto filters after 12 h of photochemical aging. 500 and 800 ∘C were selected to simulate smoldering and flaming combustion, respectively, and to cover a range of combustion conditions. Methanol extracts from Teflon filters were analyzed by ultra-performance liquid chromatography interfaced to both a diode array detector and an electrospray ionization high-resolution quadrupole time-of-flight mass spectrometer (UPLC/DAD-ESI-HR-QTOFMS) to determine the light absorption properties of biomass burning organic aerosol constituents chemically characterized at the molecular level. Few chemical or UV–visible (UV: ultraviolet) differences were apparent between samples for the fuels when combusted at 800 ∘C. Differences in single-scattering albedo (SSA) between fresh samples at this temperature were attributed to compounds not captured in this analysis, with eucalyptol being one suspected missing component. For fresh combustion at 500 ∘C, many species were present; lignin pyrolysis and distillation products are more prevalent in eucalyptus, while pyrolysis products of cellulose and at least one nitro-aromatic species were more prevalent in acacia. SSA trends areconsistent with this, particularly if the absorption of those chromophoresextends to the 500–570 nm region. Upon aging, both show that resorcinolor catechol was removed to the highest degree, and both aerosol types weredominated by loss of pyrolysis and distillation products, though they differed in the specific compounds being consumed by the photochemical aging process. 
    more » « less
  2. Biofuels produced via thermochemical conversions of waste biomass could be sustainable alternatives to fossil fuels but currently require costly downstream upgrading to be used in existing infrastructure. In this work, we explore how a low-cost, abundant clay mineral, bentonite, could serve as an in situ heterogeneous catalyst for two different thermochemical conversion processes: pyrolysis and hydrothermal carbonization (HTC). Avocado pits were combined with 20 wt% bentonite clay and were pyrolyzed at 600 °C and hydrothermally carbonized at 250 °C, commonly used conditions across the literature. During pyrolysis, bentonite clay promoted Diels–Alder reactions that transformed furans to aromatic compounds, which decreased the bio-oil oxygen content and produced a fuel closer to being suitable for existing infrastructure. The HTC bio-oil without the clay catalyst contained 100% furans, mainly 5-methylfurfural, but in the presence of the clay, approximately 25% of the bio-oil was transformed to 2-methyl-2-cyclopentenone, thereby adding two hydrogen atoms and removing one oxygen. The use of clay in both processes decreased the relative oxygen content of the bio-oils. Proximate analysis of the resulting chars showed an increase in fixed carbon (FC) and a decrease in volatile matter (VM) with clay inclusion. By containing more FC, the HTC-derived char may be more stable than pyrolysis-derived char for environmental applications. The addition of bentonite clay to both processes did not produce significantly different bio-oil yields, such that by adding a clay catalyst, a more valuable bio-oil was produced without reducing the amount of bio-oil recovered. 
    more » « less
  3. Biomass burning organic aerosol (BBOA) is one of the largest sources of organics in the atmosphere. Mineral dust and biomass burning smoke frequently co-exist in the same atmospheric environment. Common biomass burning compounds, such as dihydroxybenzenes and their derivatives, are known to produce light-absorbing, water-insoluble polymeric particles upon reaction with soluble Fe( iii ) under conditions characteristic of aerosol liquid water. However, such reactions have not been tested in realistic mixtures of BBOA compounds. In this study, model organic aerosol (OA), meant to replicate BBOA from smoldering fires, was generated through the pyrolysis of Canary Island pine needles in a tube furnace at 300, 400, 500, 600, 700, and 800 °C in nitrogen gas, and the water-soluble fractions were reacted with iron chloride under dark, acidic conditions. We utilized spectrophotometry to monitor the reaction progress. For OA samples produced at lower temperatures (300 and 400 °C), particles (P300 and P400) formed in solution, were syringe filtered, and extracted in organic solvents. Analysis was conducted with ultrahigh pressure liquid chromatography coupled to a photodiode array spectrophotometer and a high-resolution mass spectrometer (UHPLC-PDA-HRMS). For OA samples formed at higher pyrolysis temperatures (500–800 °C), water-insoluble, black particles (P500–800) formed in solution. In contrast to P300 and P400, P500–800 were not soluble in common solvents. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) and transmission electron microscopy (TEM) were used to image P600 and determine bulk elemental composition. Electron microscopy revealed that P600 had fractal morphology, reminiscent of soot particles, and contained no detectable iron. These results suggest that light-absorbing aerosol particles can be produced from Fe( iii )-catalyzed reactions in aging BBOA plumes produced from smoldering combustion in the absence of any photochemistry. This result has important implications for understanding the direct and indirect effects of aged BBOA on climate. 
    more » « less
  4. Introduction: With the capture of the first high- resolution, in-situ images of Near-Earth Objects (NEOs) a couple of decades ago [1–4], the ubiquity of regolith and the granular nature of small objects in the Solar System became apparent. Benefiting from an increased access to high computing power, new numerical studies emerged, modeling granular structures forming and evolving as small bodies in the Solar System [5–7]. Now adding laboratory studies on granular material strength for asteroid and other small body applications [8,9], we are steadily progressing in our understanding of how regolith is shaping the interiors and surfaces of these worlds. In addition, our ever-more powerful observation capabilities are uncovering interesting dust-related phenomena in the outer skirts of our Solar System, in the form of activity at large heliocentric distances and rings [10–12]. We find that our recent progress in understanding the behavior of granular material in small body environments also has applications to the more distant worlds of Centaurs and Trans-Neptunian Objects (TNOs). Internal Strength: We currently deduce internal friction of rubble piles from the observation of large numbers of small asteroids and their rotation rates, combined with the associated numerical simulations [13,14]. In the laboratory, we study internal friction of simulant materials using shear strength measurements [8]. Combining observations, modeling, and laboratory work, the picture emerges of rubble pile interiors being composed of coarse grains in the mm to cm range. The irregular shapes of the grains lead to mechanical interlocking, thus generating the internal friction required to match observations of the asteroid population [8,9]. We find that the presence of a fine fraction in the confined interior of a rubble pile actually leads weaker internal strength [9]. Surface Strength: Deducing surface regolith strength for NEOs is usually performed via average slope measurements [15–17] or, most notably, observing the outcome of an impact of known energy [18]. In the laboratory, we measure the angle of repose of simulant material via pouring tests, as well as its bulk cohesion using shear strength measurements [8]. In some cases, this allows us to infer grain size ranges for various regions of the surface and subsurface of pictured NEOs, beyond the resolution of their in-situ images. Surface Activity: The Rosetta mission revealed that a number of activity events on comet 67P/Churyumov–Gerasimenko were linked to active surface geology, most notably avalanches and cliff collapses [19]. In addition, the role of regolith strength in asteroid disruption patterns has been inferred from numerical simulations of rotating rubble piles [20]. By studying strength differences in simulant samples, it becomes apparent that a difference in cohesion between a surface and its subsurface layer can lead to activity events with surface mass shedding, without the presence of volatiles sublimating as a driver [8]. We show that such differences in surface strength can be brought upon by a depletion in fine grains or a change in composition (e.g. depletion in water ice) and could account for regular activity patterns on small bodies, independently of their distance to the Sun. This is of particular interest to the study of Centaur activity and a potential mechanism for feeding ring systems. 
    more » « less
  5. Wildfires, which have been occurring increasingly in the era of climate change, emit massive amounts of particulate matter (PM) into the atmosphere, strongly affecting air quality and public health. Biomass burning aerosols may contain environmentally persistent free radicals (EPFRs, such as semiquinone radicals) and redox-active compounds that can generate reactive oxygen species (ROS, including ·OH, superoxide and organic radicals) in the aqueous phase. However, there is a lack of data on EPFRs and ROS associated with size-segregated wildfire PM, which limits our understanding of their climate and health impacts. We collected size-segregated ambient PM in Southern California during two wildfire events to measure EPFRs and ROS using electron paramagnetic resonance spectroscopy. EPFRs are likely associated with soot particles as they are predominantly observed in submicron particles (PM 1 , aerodynamic diameter ≤ 1 μm). Upon extraction in water, wildfire PM mainly generates ·OH (28–49%) and carbon-centered radicals (∼50%) with minor contributions from superoxide and oxygen-centered organic radicals (2–15%). Oxidative potential measured with the dithiothreitol assay (OP-DTT) is found to be high in wildfire PM 1 , exhibiting little correlation with the radical forms of ROS ( r 2 ≤ 0.02). These results are in stark contrast with PM collected at highway and urban sites, which generates predominantly ·OH (84–88%) that correlates well with OP-DTT ( r 2 ∼ 0.6). We also found that PM generated by flaming combustion generates more radicals with higher OP-DTT compared to those by smoldering or pyrolysis. 
    more » « less