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At least 55 records · Page 3

Techno-economic analysis of biomass value-added processing informed by pilot scale de-ashing of paper sludge feedstock

Paper sludge biomass represents an underutilized feedstock rich in pulped and processed cellulose which is currently a waste stream with significant disposal cost to industry for landfilling services. Effective fractionation of the cellulose from paper sludge presents an opportunity to yield cellulose as feedstock for value-added processes. A novel approach to cellulose fractionation is the sidehill screening system, herein studied at the pilot-plant scale. Composition analysis determined ash removal and carbohydrate retention of both sidehill and high-performance benchtop screening systems. Sidehill screening resulted in greater carbohydrates retention relative to benchtop screening (90% vs 66%) and similar ash removal (95% vs 98%). Techno-economic analysis for production of sugar syrup yielded a minimum selling price of $331/metric ton of sugar syrup including disposal savings, significantly less than a commercial sugar syrup without fractionation. Furthermore, sensitivity analysis showed that screening conditions played a significant role in economic feasibility for cellulosic yield and downstream processes.

09 BIOMASS FUELS↗

Novel Strategy To Analyze Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Data of Biomass Pyrolysis Oil for Oligomeric Structure Assignment

Among the most prominent challenges for the analysis of biomass pyrolysis products is the characterization of the abundant oligomer fraction of bio-oil. This fraction is principally made up of pyrolytic lignins and dehydrated, highly modified sugar oligomers, called humins, in liquid phase. An emerging technique for analysis of this oligomer fraction is high-resolution Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS), which allows for accurate determination of C x H y O z formulae for detected oligomers. Additionally, using simple dehydration and fragmentation reaction schemes, similar formulae can be developed from cellulose-, hemicellulose- and lignin-derived oligomers, which are primary depolymerization products. In this paper, FT-ICR MS analysis is coupled with combinatoric dehydration and fragmentation modeling in order to match experimentally detected bio-oil oligomers with hypothetical pathways for their formation during pyrolysis. In this way, we present a novel strategy by which oligomeric structures can be proposed for bio-oils. Using this approach, it becomes possible to advance the understanding of both the molecular structures comprising the bio-oil oligomer fraction and the pathways by which these structures form during biomass pyrolysis reactions.

09 BIOMASS FUELS↗

Effective Biomass Fractionation through Oxygen-Enhanced Alkaline–Oxidative Pretreatment

The high recalcitrance of plant cell walls is an obstacle for effective chemical or biological conversion into renewable chemicals and transportation fuels. Here, we investigated the utilization of both oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) as co-oxidants during alkaline-oxidative pretreatment to improve biomass fractionation and increase enzymatic digestibility. The oxidative pretreatment of hybrid poplar was studied over a variety of conditions. Employing O 2 in addition to H 2 O 2 as a co-oxidant during the two-stage alkaline pre-extraction/copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in a substantial improvement in delignification relative to using H 2 O 2 alone during the second-stage Cu-AHP pretreatment, leading to high overall sugar yields even at H 2 O 2 loadings as low as 2% (w/w of original biomass). The presence of H 2 O 2 , however, was both critical and synergistic. Performing analogous reactions in the absence of H 2 O 2 resulted in approximately 25% less delignification and a 30% decrease in sugar yields. Here, the lignin isolated from this dual oxidant second stage had high aliphatic hydroxyl group content and reactivity to isocyanate, indicating that it is a promising substrate for the production of polyurethanes. To test the suitability of the isolated lignin as a source of aromatic monomers, the lignin was subjected to a sequential Bobbitt’s salt oxidation followed by formic-acid catalyzed depolymerization process. Monomer yields of approximately 17% (w/w) were obtained, and the difference in yields was not significant between lignin isolated from our Cu-AHP process with and without O 2 as a co-oxidant. Thus, the addition of O 2 did not lead to significant lignin crosslinking, a result consistent with the two-dimensional heteronuclear single-quantum coherence (2D HSQC) NMR spectra of the isolated lignin.

09 BIOMASS FUELS↗

Extraction of Furfural and Furfural/5-Hydroxymethylfurfural from Mixed Lignocellulosic Biomass-Derived Feedstocks

We present a combined in silico and experimental study on the extraction of furfural and 5-hydroxymethylfurfural (HMF) in aqueous–organic biphasic systems. We predict the liquid–liquid equilibria and furfural/HMF partition coefficients of over 2200 water-organic biphasic systems using the multiscale COSMO-RS model and measure experimentally single-component (furfural) and mixture (furfural and HMF) partition coefficients at room and dehydration reaction-relevant temperatures in 28 solvents. We find the experimental data to be within a factor of 2 from the COSMO-RS predictions. Even though furfural and HMF have chemical similarity, the slight differences in molecular structure render the separation of furfural easier by the supply of more solvents of higher partition coefficient for extraction. We leverage this molecular difference and experimentally demonstrate that with an additional extraction step, using dichloromethane or toluene, we can selectively extract furfural from furfural-HMF mixtures, which can coexist in lignocellulosic biomass dehydration products, despite their partition coefficients being generally correlated. We complement solvent selection criteria for biphasic lignocellulosic biomass processes with a simple mass balance extraction model for determining volume ratios in multistage extraction. Lastly, the molecular nature of the preferential furfural extraction is rationalized using COSMO-RS σ-profile analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Technical Track on Biomass Carbon Removal and Storage (BiCRS): Mapping bioresources, phase 1 - Consistency check comparing Mission Innovation’s Data Visualization Tool for Bioresources and the Clean Energy Ministerial Biofuture Initiative Global Biomass data accessible via the US Department of Energy’s Bioenergy Knowledge Discovery Framework (KDF)

The Mission Innovation (MI) Carbon Dioxide Removal (CDR) Mission, Technical Track on Biomass Carbon Dioxide Removal and Storage (BiCRS), has produced a biomass resource database for its members. In parallel, Oak Ridge National Laboratory (ORNL) developed the International Feedstock Reporting data portal—herein referred to as the CEM Biofuture-KDF data—on behalf of the Clean Energy Ministerial Biofuture Initiative (CEM Biofuture), as a specific task under Biofuture’s 2024–25 Action Plan. This work was conducted at the request of CEM Biofuture and funded by the U.S. Department of Energy in support of that initiative, and it is hosted within DOE’s Knowledge Discovery Framework (KDF).

09 BIOMASS FUELS↗

A Seasonal Trend of Single Scattering Albedo in Southern African Biomass-burning Particles: Implications for Satellite Products and Estimates of Emissions for the World's Largest Biomass-burning Source

As a representative site of the southern African biomass-burning region, sun-sky data from the 15 year Aerosol Robotic Network (AERONET) deployment at Mongu, Zambia, was analyzed. For the biomass-burning season months (July-November), we investigate seasonal trends in aerosol single scattering albedo (SSA), aerosol size distributions, and refractive indices from almucantar sky scan retrievals. The monthly mean single scattering albedo at 440 nm in Mongu was found to increase significantly from approx.. 0.84 in July to approx. 0.93 in November (from 0.78 to 0.90 at 675 nm in these same months). There was no significant change in particle size, in either the dominant accumulation or secondary coarse modes during these months, nor any significant trend in the Angstrom exponent (440-870 nm; r(exp 2) = 0.02). A significant downward seasonal trend in imaginary refractive index (r(exp 2) = 0.43) suggests a trend of decreasing black carbon content in the aerosol composition as the burning season progresses. Similarly, burning season SSA retrievals for the Etosha Pan, Namibia AERONET site also show very similar increasing single scattering albedo values and decreasing imaginary refractive index as the season progresses. Furthermore, retrievals of SSA at 388 nm from the Ozone Monitoring Instrument satellite sensor show similar seasonal trends as observed by AERONET and suggest that this seasonal shift is widespread throughout much of southern Africa. A seasonal shift in the satellite retrieval bias of aerosol optical depth from the Moderate Resolution Imaging Spectroradiometer collection 5 dark target algorithm is consistent with this seasonal SSA trend since the algorithm assumes a constant value of SSA. Multi-angle Imaging Spectroradiometer, however, appears less sensitive to the absorption-induced bias.

aerosol absorption↗

Quantitative Determination of Biomass-derived Renewable Carbon in Fuels from Coprocessing of Bio-oils in Refinery Using a Stable Carbon Isotopic Approach

Increasing renewable carbon incorporation into conventional fuels through coprocessing with vacuum gas oil (VGO, a petroleum refining feedstock) is a critical step in biofuels development, scaling-up, adoption and associated GHG reduction. Optimization of the co-processing parameters maximizes incorporation of the renewable carbon in the fuel products. Quantitative determination of the renewable carbon content in the co-processed products provides direct evaluation of the parameters. The co-processing bio-oil with VGO through hydrocracking (HC) or fluid catalytic cracking (FCC) system resulted in carbon isotopic fractionation that prevented the direct use of the isotope mixing model for quantifying the renewable carbon. Here, we report an algorithm of using a stable carbon isotope approach to quantify the renewable carbon content in co-processing biofuel products through high-precision ?13C analysis. A controlled experiment carried out by blending a fossil diesel (-29.013‰) with a bio-diesel (-30.099‰) at various blending levels up to 98.0/2.0 wt% is presented and has demonstrated the applicability of this approach. The carbon isotope fractionation factors for the bio-oil co-processing were obtained by using a 14C-derived isotope-mixing model. The ?13C method was tested by co-processing 13C-labeled bio-crude and natural woody biomass-derived fast pyrolysis (FP) and catalytic fast pyrolysis (CFP) bio-oils with VGO. The results were verified by 14C accelerator mass spectrometry (AMS) method (ASTM-D6866) and compared with the yield mass balance (YMB) method. Strong agreement between d13C and 14C AMS methods demonstrated the applicability of the ?13C method to quantify renewable carbon content in co-processing fuel products and guide the co-processing optimization

Li, Zhenghua↗

Screening and evaluation of biomass upgrading strategies for sustainable transportation fuel production with biomass-derived volatile fatty acids

Biomass conversion to fuels and chemicals is crucial to decarbonization, but choosing an advantageous upgrading pathway out of many options is challenging. Rigorously evaluating all candidate pathways (process simulation, product property testing) requires a prohibitive amount of research effort; even simple upgrading schemes have hundreds of possible permutations. We present a method enabling high-throughput screening by approximating upgrading unit operations and drop-in compatibility of products (e.g., fuel properties) and apply it to volatile fatty acid (VFA) conversion to liquid transportation fuels via a MATLAB script, VFA Upgrading to Liquid Transportation fUels Refinery Estimation (VULTURE). VULTURE selects upgrading configurations that maximize fuel blend bio-derived content. We validate VULTURE's approximations through surrogate fuel property testing and process simulation. Techno-economic and life cycle analyses suggest that VFA upgrading processes down-selected by VULTURE are profitable and have low carbon intensities, demonstrating the potential for the strategy to accelerate process development timelines at decreased costs.

09 BIOMASS FUELS↗

Chemical Imaging of Atmospheric Biomass Burning Particles from North American Wildfires

The effects of biomass burning aerosols (BBA) on radiative forcing and cloud formation depend on chemical composition and the internal structures of individual particles within smoke plumes. To improve our understanding of the chemical and physical properties of BBA emitted at different times of the day and their evolution during atmospheric aging, we conducted a study as a part of the Fire Influence on Regional to Global Environments and Air Quality field campaign. Particle samples were collected onboard a research aircraft from smoke plumes from a wildfire in eastern Oregon during late afternoon and nighttime flights on August 28, 2019. A time-resolved aerosol collector was used to collect samples on substrates for offline spectromicroscopic imaging to investigate the single-particle characteristics of BBA particles. Approximately 20,400 individual particles from 10 selected samples were analyzed using computer-controlled scanning electron microscopy coupled with energy-dispersive X-ray microanalysis, revealing their elemental composition, morphology, and viscosity. Elemental microanalysis indicated that aged potassium is likely found in the form of K 2 SO 4 , KNO 3 , and possible K-organic salts. Further chemical speciation and carbon bonding mapping within individual particles were conducted using synchrotron-based scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Real-time, water-soluble light absorption measurements were acquired using a particle-into-liquid sampler instrument coupled to a liquid waveguide capillary cell and total organic analyzer. In the late afternoon samples, 65% of the total particle number population consisted entirely of organic components, compared to 46% in the nighttime particles. These differences were attributed to discrepancies in composition at the time of emission and to the daytime condensation and accumulation of photochemically formed secondary organic material on existing BBA particles, a process that halts at night. Microscopy images indicated that particle viscosity was lower in the nighttime particles (<10 1 Pa·s), likely due to increased relative humidity and a higher contribution from hygroscopic inorganic components. The chemical heterogeneity of individual particles was quantified using STXM-derived mixing state parameters. The nature of carbon bonding within individual particles was inferred from the extent of carbon sp 2 hybridization derived from NEXAFS spectra. Average percentages of sp 2 hybridization range between 40% and 60%, with no noticeable differences between late afternoon and nighttime flights. These findings were compared with the online optical properties of both late afternoon and nighttime smoke plumes, providing valuable insights into the complex relationship between chemical composition and optical properties of BBA particles at different times of the day.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective and Efficient Production of Biomass-Derived Vinylfurans

We describe a two-step catalytic process for the selective and rapid conversion of biomass-derived acetylfurans into vinylfurans. This is accomplished by nearly quantitatively reducing acetylfurans into furyl alcohols using a copper chromite catalyst and exploiting the promoter-like properties of ethanol, the solvent. Subsequently, furyl alcohol is dehydrated using solid-acid catalysts. Catalyst deactivation due to oligomeric species is a major issue, but the activity can be partially recovered by calcination. Optimization of reaction conditions showed that the selectivity could be increased by using nitrobenzene, a polar aprotic solvent. Here, the high-boiling point solvent allows the formation of vinylfurans with a selectivity of up to 85%; the product can be isolated in high purity by distillation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MgO(111) Nanocatalyst for Biomass Conversion: A Study of Carbon Coating Effects on Catalyst Faceting and Performance

Solid base metal oxide catalysts such as MgO offer utility in a wide variety of syntheses from pharmaceuticals to fuels. The (111) facet of MgO shows enhanced, unique properties relative to the other facets. Carbon coatings have emerged as a promising modification to impart metal oxide catalyst stability. Here, we report the synthesis, characterization, and catalytic properties of commercial MgO, MgO(111), and carbon coated derivatives thereof for 2-pentanone condensation. The dimer and trimer products of this reaction can be used as precursors for biofuels upon oxygen removal and thus have relevance in environmental sustainability. Additionally, MgO(111) maintained impressive selectivity towards the dimer product after carbon coating, whereas the other catalysts experienced a decrease in conversion and selectivity as a consequence of the carbon coating. Our findings highlight the catalytic efficacy of MgO(111), provide insight into carbon coating for catalyst stability, and pave the way for continued mechanistic investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗