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At least 523 records · Page 29

Upcycling linear low-density polyethylene waste to turbostratic graphene for high mass loading supercapacitors

Linear low-density polyethylene (LLDPE) waste is difficult to upcycle into more valuable carbon materials because it tends to completely decompose into small molecules during thermal processing. In this work, LLDPE is upcycled into a high quality turbostratic graphene using a pre-treatment step to oxidatively crosslink the polymer with the assistance of solid additives (KCl and K 2 CO 3 ) that improve crosslinking by increasing the effective surface area of the polymer melt during processing. After this pretreatment step, the crosslinked polymer could then be carbonized and catalytically graphenized between 400–950°C without decomposition of the polymer feedstock. The LLDPE derived graphene (LLDPE-G) obtained from this process has a Brunauer–Emmett–Teller (BET) specific surface area, up to 1800m 2 g -1 and average Raman I D /I G and I 2D /I G ratios of 0.85 and 0.57, respectively, indicating high quality graphene. When used as an electrode material in symmetric supercapacitors, LLDPE-G possesses a specific capacitance up to 175Fg -1 at a mass loading of 20mgcm -2 , which is two times the commercial requirement, yielding an areal capacitance of 3.5 Fcm -2 . Moreover, LLDPE-G exhibits exceptional cycling stability with a capacitance retention of 95.8 % after 100,000 cycles at a current density of 4.0 Ag -1 . Additionally, the KCl and K 2 CO 3 solids are recycled and reused over 3 complete reaction cycles to make new LLDPE-G with the material quality and electrocapacitive performance retained and verified after each cycle. Our approach creates new opportunities for upcycling waste LLDPE and other varieties of polyethylene into a higher value graphene used for electrochemical energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membrane-based solvent extraction for the recovery of rare earths from phosphate mining process streams

This study reports on the capture of rare earth elements (REEs) from phosphate industry process streams, including phosphoric acid (PA) sludge and phosphogypsum (PG), using a membrane solvent extraction (MSX) process. While MSX has been proven effective for a relatively concentrated feed, its effectiveness for dilute REEs solutions remains unexplored. Investigated PA-sludge and PG particles contain total REEs concentrations of ∼1100 and ∼320 ppm, respectively. Acid leaching, implemented to dissolve the REEs, significantly dilutes the REEs concentration to ∼210 ppm for PA-sludge leachate and ∼60 ppm for PG leachate. These low concentrations, compounded by the higher levels of non-REE ions and radioactive species, uranium (U) and thorium (Th), poses challenges to the MSX process. Here, we demonstrated that N,N,N′,N′-tetraoctyl-diglycolamide (TODGA) selectively binds REEs from a >3 M nitric-acid leachate while effectively rejecting U and Th. Concentrations of light REEs in strip solution were doubled compared to the feed, while heavy REEs were preferentially extracted. Furthermore, >99% purity gypsum, free of U and Th, was precipitated during the acid leaching process, aiding separation by removing significant amounts of non-REEs species (e.g., calcium) prior to the MSX process. Molecular simulations support the experimental data, suggesting preferential separation of heavy over light REEs. Based on these results, a cost-effective integrated process including pretreatment, acid leaching, MSX, and wastewater treatment is proposed for the co-recovery of REEs, phosphoric acid, gypsum, and U. This study shows MSX as a technically and economically feasible process for the recovery of REEs from low-concentration process streams, offering advantages over conventional solvent extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ineffectiveness of ultrasound at low frequency for treating per- and polyfluoroalkyl substances in sewage sludge

Concerns have been raised about per- and polyfluoroalkyl substances (PFAS) in sewage sludge given the urgent need of finding suitable disposal methods for sludge. Here in this study, we evaluated the effect of ultrasonication on PFAS changes in sewage sludge. It was revealed that although ultrasonication at 20 kHz increased the soluble chemical oxygen demand (SCOD) of treated sewage sludge, this technique was ineffective for degrading perfluoroalkyl acids (PFAAs) and their precursors. Ultrasonic treatment for longer time (>15 min) led to concentration increase of perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), and perfluorohexanoic acid (PFHxA) in the liquid phase, possibly due to their release from disrupted sludge flocs during cavitation. Adding permanganate (10 mM) to the ultrasonic system could also enhance the disruption of sludge particles, resulting in higher concentrations of PFOA and PFHxA in the solid phase and PFOA, PFHpA, PFHxA, and perfluorobutanesulfonic acid (PFBS) in the liquid phase. Overall, ultrasonic pretreatment at 20 kHz and 0.7 W/mL is unlikely to remove PFAS from sewage sludge. Instead, it could increase the risk of PFAS pollution upon final sludge disposal. Effective treatment technologies are thus demanded if PFAS in sludge are regulated.

54 ENVIRONMENTAL SCIENCES↗

Determination of transition metal ions in fossil fuel associated wastewaters using chelation ion chromatography

Here, this study outlines the development and subsequent validation of a method using chelation ion chromatography (CIC) pretreatment followed by traditional ion chromatography (IC) and post column UV/vis detection to measure transition metals in fossil fuel wastewaters, such as oil & gas (O&G) brines and coal mine drainage (CMD) waters. Measurement of transition metals is often an important characterization step in the research of environmental and energy systems. IC represents one way to measure these metals with the advantages of being versatile, simple and relatively low cost compared to other analytical methods. However, high concentrations of alkali and alkaline earth metals present in fossil fuel wastewaters will decrease IC detectability of transition metals in these waters. In this study, a CIC method was developed for the analysis of transition metal ions (Fe 3+ , Cu 2+ , Ni 2+ , Zn 2+ , Co 2+ , Mn 2+ , and Fe 2+ ) in fossil fuel associated wastewaters such as Appalachian CMD and O&G wastewaters from the Permian and Bakken shale basins in the United States. CIC system incorporated an on-line chelator column (e.g., the MetPac CC-1) with high selectivity for transition metals over alkali and alkaline earth metals for salt matrix removal prior to transition metal separation and detection. Additional method developments also included acidifying all samples to 2% v/v HCl and using gradient elution rather than isocratic. The recoverability of transition metals in simple salt solutions commonly found in CMD and brine samples (e.g. NaCl, Na 2 SO 4 , CaCl 2 ) using CIC was evaluated and compared to that using traditional IC. Our results found that the CIC system significantly improved transition metal recoveries for samples in 10,000 mg/L CaCl 2 matrix, reaching 87%-108% recovery for all analytes, as opposed to 2-323% recovery in traditional IC. The limits of detection in this study achieved 10.09 – 161.2 μg/L, comparable to reported values in similar IC studies. The developed method was also verified with certified water samples, resulting in 89% - 111% recoveries in samples with higher analyte concentrations (i.e. >4x the LoDs). The developed method achieved 87% -112% recoveries for most analytes in CMD samples and 72%-138% recoveries for Bakken shale samples, relative to ICP-MS values. Overall, the current IC method can be a very good screening tool for fast and cheap analysis for transition metals at mg/L level, to facilitate selection of samples for more detailed ICP-MS analysis.

01 COAL, LIGNITE, AND PEAT↗

Laboratory and pilot-scale studies of membrane distillation for desalination of produced water from Permian Basin

Substantial quantities of produced water generated during the extraction of oil and gas from unconventional reservoirs present significant environmental concern and increase the operating cost for this industry. Membrane Distillation (MD) can serve as a potential solution for beneficial reuse of produced water by generating high-quality permeate and reducing the volume of produced water requiring disposal. This study investigated treatment of produced water from Permian Basin in both laboratory and pilot-scale studies. Laboratory tests revealed the potential to successfully recover 50% of produced water although some increase in permeate conductivity was observed due to the passage of ammonia from the feed side. Initial pilot-scale test with filtration of raw produced water as the only pre-treatment step led to precipitation of SrSO 4 , NaCl, and Fe in the system once the solubility limits for these salts were exceeded. However, chemical pretreatment that included pH adjustment, aeration, and barite precipitation, allowed successful steady-state operation of the AGMD pilot system for 5 days where the produced water was concentrated from 127 g/L to 255 g/L (~50% water recovery) while recovering high quality permeate. Overall, greater than 99.7 % salt rejection was achieved with the average permeate flux of 1.86 LMH. Finally, mass balance analysis suggested potential Ba and Ca precipitation in the system but there was no impact on AGMD performance and permeate quality during 5 days of continuous operation in the field.

42 ENGINEERING↗

Scaling dynamics in low-salt-rejection reverse osmosis for high-salinity produced water desalination: Mechanistic modeling and membrane autopsy

Membrane scaling remains a critical barrier to the reliable operation of desalination systems, particularly for hypersaline produced water (PW) treatment. This study fills the knowledge gap of autopsy-based model validation for PW desalination by elucidating scaling mechanisms in a Low-Salt-Rejection Reverse Osmosis (LSRRO) system through the integration of pilot-scale experimentation and complementary modeling approaches. A semi-empirical modeling framework was developed and applied to a multistage pilot LSRRO system equipped with nanofiltration and RO membranes treating high-salinity PW from the Permian Basin. Water quality analysis showed that total dissolved solids decreased from ~130,000 mg/L to ~1900 mg/L in the permeate, then further reduced to ~300 mg/L by a second-pass RO. Two different thermodynamic modeling approaches were evaluated: the first extends the LSRRO framework by incorporating system complexity and scaling phenomena, whereas the second method explicitly captures concentration polarization in localized supersaturation. Both methods illustrate the tendency for carbonate and sulfate scaling throughout the stages. Membrane autopsies revealed a silica-dominated deposit matrix, localized CaSO 4 at Stage 2, and minor barite/celestite despite their prominence in model predictions. Quantum-chemical calculations indicated silica scaling can be rationalized by favorable adsorption of H 4 SiO 4 on Fe-oxide surfaces (ΔG ≈ −44 kJ/mol), providing a kinetic pathway for interfacial inorganic polymerization even when bulk equilibrium predictions are conservative. Overall, the thermodynamic scaling modeling and membrane autopsy revealed heterogeneous, localized deposits with limited impact on LSRRO performance, while quantum analysis rationalized the thermodynamically unfavorable precipitation formation under bulk equilibrium, reconciling model–autopsy discrepancies. These insights support targeted pretreatment and silica-specific antiscalants to extend membrane lifetime and increase recovery, providing a transferable framework for hypersaline water desalination systems. The combined experimental–computational approach provides new mechanistic insight into scaling in hypersaline membrane systems and establishes a transferable framework for predicting and mitigating scaling in next-generation desalination technologies.

Low-salt-rejection reverse osmosis↗

Unraveling the nature of sulfide ions in hydrometallurgical recycling of NCM622 cathode material

The use of lithium-ion batteries (LIBs) has increased dramatically since its initial inception in the late 20th century. Such a surge in the LIB market and industry has resulted in a huge demand for mineral resources. Besides, the large scale of production will lead to massive amounts of waste batteries in the end. As such, recycling is seen as an end-of-pipe process to resolve sustainability and environmental concerns. The hydrometallurgical recycling is considered to be the most prominent method to recover cathode materials from spent LIBs owing to its high leaching efficiency and low energy costs. A series of procedures including pretreatment of the spent LIBs, acid leaching of the black mass, chemical co-precipitation of the hydroxide precursor, and sintering of the cathode active material need to be operated precisely. In this aspect, the impurities introduced during the process could pose a serious threat to the reaction stability as well as recycling consistency. Here, the impact of sulfide ions on recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode material with the method of hydrometallurgy is first investigated in detail. This study shows that hydrometallurgical process is not obviously influenced by sulfide impurity. No signs of secondary phase or impurity inclusion are spotted in synthesized cathodes. Under 5 at % sulfide concentration conditions, the obtained NCM622 cathode exhibits a capacity of 159.4 mAh/g after 100 cycles at 1/3C, which is at the same level as virgin benchmark. The difference in rate performance between cathodes with and without additional sulfide is less than 2 % or even smaller. In short, the results indicate a neutral status of sulfide ions in hydrometallurgical recycling.

25 ENERGY STORAGE↗

Reduction of selenite by bacterial exudates

Bacterial reduction of Se(IV) is a significant component of the global selenium cycle, and hence affects the fate and transport of selenium in both natural and contaminated environments. However, it is unknown whether bacterially-produced exudates are capable of reducing selenium independent of bacterial cells. In this study, we measured the rate and extent of Se(IV) reduction by exudates from three bacterial species, and we determined the importance of exudate sulfhydryl sites by conducting parallel experiments after treatment of the exudates with a sulfhydryl-specific blocking molecule. Here, we also conducted experiments with whole cell biomass for each of the three bacterial species to determine the importance of exudate-only reduction relative to whole biomass-promoted reduction. Under our experimental conditions, exudates from Bacillus subtilis and Pseudomonas putida remove Se(IV) from solution after an approximately 20-24 h lag period, but exudates from Shewanella oneidensis are ineffective at Se(IV) removal, except when the cells are grown in the presence of Se(IV). For both B. subtilis and P. putida , pretreatment blocking of the sulfhydryl sites on the exudate molecules dramatically decreases the rate and extent of Se(IV) removal, strongly suggesting that sulfhydryl groups on the exudate molecules play a key role in the Se(IV) reduction mechanism. The behavior of S. oneidensis exudates indicates that up-regulation of the Se(IV) reduction mechanism can occur in response to the Se content of the medium in which the cells grow. Our results demonstrate the capacity of some bacterial exudates to reduce Se(IV), and suggest that the activity of bacterial exudates should be accounted for when modeling selenium cycling in natural and engineered environments.

59 BASIC BIOLOGICAL SCIENCES↗

Selective leaching and solvent extraction of Lithium from spent batteries

Pre-extracting Li from spent lithium-ion batteries (LIBs) is crucial because the recovery efficiency of Li is low after other critical metals have been extracted. Traditional methods involving black mass roasting followed by water leaching have resulted in the extraction of 76 % Li and 61 % Al. However, pre-leaching Li from pretreated black mass using an oxalic acid solution at both ambient and elevated temperatures significantly improved results, achieving 98.1 % Li, 99.5 % Al, and 100 % Fe extraction while leaving Ni, Co, Mn, and Cu behind under optimal conditions. Oxalic acid crystals were recovered by refrigerating the leach solution at temperatures below 5 °C and were reused with nearly identical leaching efficiency. Selective extraction of Li from the oxalate leach solution was achieved using Cyanex® 936P under optimal conditions. Here, due to its extremely low Li extraction efficiency, Dichloromethane proved unsuitable as a diluent. Comparative extraction tests using Cyanex® 936P, Cyanex® 272, and DEHPA in kerosene demonstrated that Cyanex® 936P is an excellent extractant for Li, effectively separating it from other impurities. Under optimal conditions, 98.8 % of available Li was extracted using 20 % Cyanex® 936P, compared to 51.1 % with Cyanex® 272 and 39.9 % with DEHPA in kerosene. Additionally, stripping Li from Cyanex® 936P using H 2 SO 4 and HCl was explored, with HCl yielding the best performance.

Black mass↗

Tunable structure and reinforcement of polyvinyl alcohol (PVA) hydrogels using fungal chitin particles

Polysaccharides, including chitin, are one of the most abundant biopolymers in nature and are increasingly recognized as a sustainable alternative to petroleum-derived plastics and synthetic fillers in polymer composites. Traditionally sourced from crustacean shells, chitin offers mechanical strength and biocompatibility with limitations also in processability and functionality. Fungal-derived chitin material represents a promising alternative, with advantages including scalable fermentation on low-cost substrates, absence of shellfish allergens, and tunable molecular architectures that vary by species, developmental stage, and growth environment. Here, in this study, we systematically examined chitinous materials obtained from taxonomically and functionally distinct fungi, Laccaria bicolor, Trichoderma reesei and Rhizopus oryzae, to assess their structural, chemical, and morphological properties as reinforcement agents in polymer composites. Mild alkaline pretreatment was employed to obtain mycelium chitin particles, thereby improving accessibility to chitin and co-occurring β-D-glucans while maintaining microparticle integrity. Comprehensive FTIR and solid-state NMR analyses revealed species-specific differences in chemical composition and microstructure, with R. oryzae exhibiting a unique spectral signature. These fungal-derived chitin were then incorporated into poly(vinyl alcohol) (PVA) hydrogels, where they acted as reinforcing fillers without the need for additional chemical crosslinkers. Comparative evaluation of hydrogel properties demonstrated that fungal chitin significantly enhanced mechanical performance, with all mycelium fillers mitigating the water weakening in PVA hydrogels. R. oryzae-derived composites tripled the hydrogel tensile strength while the submicron fibrous morphology in L. bicolor contributes to over 45 % tensile improvement in dry PVA composites. Our findings highlight the potential of fungal biomass as a tunable, sustainable platform for producing chitin-based reinforcing agents.

Chitin↗

Conclusions from 3 years of continuous capture plant operation without exchange of the AMP/PZ-based solvent at Niederaussem – insights into solvent degradation management

A many times heard mantra of solvent degradation management in amine-based post combustion capture is “keep the solvent clean” to minimize solvent consumption. It is assumed that the amine losses would decrease by the removal of metals, degradation products, and reactive trace components which are captured from the flue gas, like NO 2 (as potentially driving components of the amine degradation besides dissolved O 2 ). However, this theoretical hypothesis – based on results from laboratory experiments typically generated with fresh amines – disregards the complexity of the solvent matrix, interaction of potential metal catalysts with degradation products and oxidizing agents, and specific chemical requirements which must be fulfilled before a degradation mechanism can proceed. Degradation of the solvent CESAR1 (aqueous solution of 3.0 molar 2-amino-2-methylpropan-1-ol (AMP) and 1.5 molar piperazine (PZ)) is investigated in a unique long-time test campaign (testing time up to now 40 months; 24/7 operation) without replacement of the solvent inventory at the capture pilot plant at the lignite-fired power plant in Niederaussem. Three solvent management strategies with different effect mechanisms are investigated and evaluated: (a) removal of only anionic compounds and trace elements (within 75 days solvent inventory treated two times) and anionic as well as cationic compounds and trace elements (114 days, inventory treated four times) from the solvent by ion exchange, (b) adsorptive removal of trace elements from the solvent by active carbon in 35% of the operating time, and (c) removal of >80% NO 2 by flue gas pretreatment with thiosulfate/sulfite solution (dosing for 2,000 h). The results of the testing program clearly show that “solvent cleanliness” is not a well-defined parameter and that results from laboratory tests, tests without fully representative industrial flue gasses, and short-term testing of monoethanolamine cannot be generalized for other solvents and industrial application. Furthermore, these results showcase that specific degradation management considering solvent, capture plant and flue gas quality is reasonable. Overshooting efforts for solvent management are contra-productive and produce unnecessary waste streams, efficiency losses and costs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mithramycin A Radiosensitizes EWS:Fli1+ Ewing Sarcoma Cells by Inhibiting Double Strand Break Repair

The oncogenic EWS:Fli1 fusion protein is a key transcriptional mediator of Ewing sarcoma initiation, progression, and therapeutic resistance. Mithramycin A (MithA) is a potent and specific inhibitor of transcription mediated by the EWS:Fli1. We tested the hypothesis that pretreatment with MithA could selectively radiosensitize EWS:Fli1{sup +} tumor cells by altering the transcriptional response to radiation injury.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Interprofessional Image Verification Workshop for Physician and Physics Residents: A Multi-Institutional Experience

Verification of patient position through pretreatment setup imaging is crucial in modern radiation therapy. As treatment complexity increases and technology evolves, physicist-physician collaboration becomes imperative for safe and successful radiation delivery. Despite the importance of both, residency programs lack formal interprofessional education (IPE) activities or structured training for image verification. Here we show the impact of an interprofessional image verification workshop for residents in a multi-institutional setting.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

The physiochemical alteration of flax fibers structuring components after different scouring and bleaching treatments

Scouring and bleaching are essential steps in flax yarn production; however, in many cases, these treatments have relatively low selectivity on non-cellulosic polysaccharides (NCPs) and lignin. Herein, the specific chemical properties of flax fibers through a variety of scouring and/or bleaching procedures are reviewed to understand their correlations with the mechanical and morphological characteristics. The hydrolysis behaviors of hemicellulose and lignin are different from those of cellulose during chlorine-alkali-oxygen (Cl-AO), enzyme-alkali-oxygen (EAO), and alkali-oxygen (AO) treatments, while the structural hemicellulose polysaccharides fractions were not affected by acid pretreatment followed by alkali scouring (AA) treatment. It was found that the unbleached AA treatment improved scouring efficiency to the greatest extent by decreasing 73.3 % of hemicellulose content and 59.8 % of lignin content compared to the untreated flax fibers and obtained the highest tensile strength (6.58 cN/dtex) and elongation (3.73 %). Delignification was more crucial on fiber tenacity and fineness than hemicellulose removal (R 2 = 0.71, 0.79 vs R 2 = 0.46, 0.61). Within the hemicellulose fractions, a corresponding beneficial relationship between the xylan (XYL) composition and flax fiber properties is presented. The correlation of GM and GGM contents in hemicellulose with flax fiber length was significant with R 2 value 0.97 and 0.99, respectively. This work provides insight into the hydrolysis behavior of hemicellulose and a basis for developing scouring and/or bleaching models that can predict fiber properties.

60 APPLIED LIFE SCIENCES↗

Beneficial effect of surfactant in adsorption/desorption of lignocellulose-degrading enzymes on/from lignin with different structure

Nonionic surfactant Tween 80 is effective in alleviating the adsorption of lignocellulose-degrading enzymes onto lignin. However, the impacts of lignin structural characteristics on this mitigation effect of Tween 80 were still not clear. Herein, effects of Tween 80 on cellulase and xylanase adsorption on different enzymatic residual lignins (ERLs) and poplar samples were investigated. Besides, effects of Tween 80 on desorption of the two enzyme preparations from different ERLs and poplar samples were also evaluated. By adding Tween 80, the inhibition of ERLs to cellulase hydrolysis was offset and the positive role of Tween 80 in Avicel hydrolysis with presence of ERLs was more effective. Binding strength of cellulase with ERLs was alleviated from 236.0 – 410.9 to 43.9 – 116.6 mL/g after adding 0.5 mg/mL Tween 80. When ERLs was more hydrophobic and had more condensed phenolic OH, the alleviation effect of Tween 80 on cellulase adsorption on ERLs was intensified but its positive effect on enhancing cellulase desorption was weakened. Tween 80 was effective in increasing xylanase activity and preventing xylanase deactivation. Further, with the increase of lignin content and phenolic OH in pretreated poplar, the effect of Tween 80 in alleviating xylanase adsorption on poplar samples was intensified but the effect in enhancing xylanase desorption from poplar samples was weakened. The results provided distinct findings to understand the interaction between Tween 80 and cellulase/xylanase in enzymatic saccharification of lignocelluloses.

59 BASIC BIOLOGICAL SCIENCES↗

Assessing microbial systems and process configurations for improved ethanol production from sugary stovers by integrating soluble sugars and holocellulose

Here, this study evaluated microbial systems and technological approaches to configure the whole slurry co-fermentation process for ethanol biosynthesis from a novel stover system rich in sugars. Two approaches, namely separate and simultaneous hydrolysis and co-fermentation (SHCF and SSCF, respectively), were investigated using Escherichia coli monoculture and E. coli-yeast coculture. The SSCF with E. coli monoculture produced 32.75 g/L ethanol, representing only 44.87% yield, which left 65.13 g/L of total sugars unconverted and exhibited limited xylose consumption. Subsequently, a coculture-based SHCF significantly enhanced sugar consumption, leading to increase in ethanol yield and concentration to 66.94% and 48.86 g/L, respectively. Nevertheless, xylose utilization remained minimal due to the preference for glucose and the inhibitory effects of certain compounds. Thereafter, modification of the medium composition by supplementing betaine and sodium metabisulfite improved ethanol production to 53.18 g/L by reducing the toxic effects of inhibitors. Finally, a dual-phase SSCF (DP-SSCF) was explored by allowing the consumption of sugars from the pretreated slurry in the first phase, followed by concurrent cellulose hydrolysis and utilization of the resulting glucose in the second phase. This strategy increased ethanol titer to 63.14 g/L, with 84.3% yield and 0.88 g/L/h productivity.

09 BIOMASS FUELS↗

The role of biochar in the degradation of sugars during fast pyrolysis of biomass

With appropriate pretreatment, sugars can be a major product from fast pyrolysis of lignocellulosic biomass. Analytical pyrolysis of pure cellulose can produce up to 60 wt% yield of levoglucosan although yields are significantly lower in continuous pyrolysis at larger scales. Secondary reactions of vaporized levoglucosan are thought to be responsible for this loss of sugar yield, suggesting changes in the design and operation of pyrolysis reactors to minimize these reactions. Micropyrolysis experiments were performed to better understand the mechanism of sugar degradation in the presence of biochar. A 57% loss in levoglucosan yield was observed for cellulose overlain with untreated biochar powder compared to the pure cellulose control sample. The addition of biochar derived from pyrolysis of untreated corn stover to a fluidized bed pyrolyzer reduced sugar yields from cellulose from 61.3 wt% to 21.3 wt% and 41.5–11.6 wt% for conventional and autothermal operation, respectively. The significant drop in sugar yield due to biochar interaction inspired change in feeder configuration for the fluidized bed pyrolyzer to reduce vapor-char interactions. Biomass feeding was changed from in-bed to above-bed injection, which allowed significant devolatilization to occur above the layer of biochar that exists at the surface of the bed. Finally, by reducing secondary reactions, bio-oil and sugar yields increased by 7.9% and 14%, respectively, for autothermal pyrolysis.

09 BIOMASS FUELS↗