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A pilot-scale continuous tubular reactor increases enzymatic digestibility of four different feedstocks by removing xylan and effectively achieving economically viable ethanol concentrations.
We developed an CFD aided ML-based tool for rapid assessment and optimization of different compositions of biomass in a fluidized bed reactor. First, we use CFD to simulate fluidized bed reactors with known inlet biomass mixtures and obtain corresponding syngas yields. A lumped kinetic mechanisms represents the conversion of cellulose, hemicellulose, and lignin, as well as subsequent cracking of tars into non-condensable gases (H 2 , CO, CO 2 , CH 4 ). We use Bayesian analysis/optimization to obtain the ideal operational and mass flow conditions for hydrogen production.
To evaluate the re-design and reconfiguration of a dual-fluidized bed (DFB) gasification system into a recirculating pyrolysis reactor, Computation Fluid Dynamic (CFD) simulations of the system were conducted. The Barracuda Virtual Reactor® computational particle fluid dynamic code was used to perform simulations of the pyrolysis process. Modeling of the chemical reaction kinetics for both gas phase and solid particle phase were included. The recirculating pyrolysis reactor shown in Fig. 1a is based on a bubbling-bed biomass pyrolyzer and a riser combustor to convert the remaining char. The operational differences in the re-configuration of the DFB gasification system into a recirculating pyrolysis system for the production of bio-oil are (1) replacement of a low-surface area inert bed material with a high-surface-area bed material that has acidic properties to provide catalytic activity for the production of bio-oil with reduced oxygen content, (2) lower temperature and residence time for bio-oil production from pyrolysis, (3) replacement of the fluidization gas in the bubbling bed pyrolyzer from steam to nitrogen, and (4) the reduction of pyrolyzer freeboard volume. The bed material used for catalytic pyrolysis is Sasol 300 (300-micron dia., bulk density 0.94 kg/l, and surface area 130 m2/g) and is a theta-alumina with mild acidity. This is in comparison with previous standard bed material Carbo HSP (430-micron dia., bulk density 2.01 kg/l, and surface area 0.03 m2/g) used for gasification. For bio-oil production, pyrolysis in the bubbling bed requires temperatures in the range of 550 C in comparison with gasification temperatures near 850 C. To attain this lower temperature requires management of the energy mass balances, with control of the bed material recirculation rate between bubbling bed pyrolyzer and riser combustor, the introduction of a nitrogen purge in the pyrolyzer, and adjusting the pressure balance between the two vessels. To extract bio-oil from the pyrolysis reactor with a snorkel, two different freeboard configurations were evaluated. In Fig. 1 b the existing high freeboard configuration is shown and in Fig. 1 c the reduced freeboard design is presented. The introduction of a nitrogen purge for the high free board configuration provided the highest bio-oil production from the CFD simulations. To decrease the bed-material circulation rate, primary and secondary air on the combustor side were reduced, and the pressure on the combustor was slightly increased. A portion of the biomass and bio-oil was observed to be transported to the combustor, leading to a smaller pyrolysis yield. The control of the pyrolyzer temperature is performed by controlling the circulation rate. Good fluidization of the bubbling bed and cascade PID control are required to keep the temperature from oscillating due to large time delay experienced when changing primary and secondary air. (a) (b) (c) Figure 1. (a) Dual Fluidized Bed pyrolysis system configuration, (b) mole fraction of nonpolar biooil in high freeboard configuration, and (c) mole fraction of nonpolar bio-oil in low freeboard configuration with nitrogen purge introduced in both configurations.
Lignocellulosic biomass conversion to renewable, carbon-neutral materials, fuels, and chemicals is the cornerstone of the transition to a sustainable future bioeconomy. Green energy in the form of electricity needs to be coupled with or substitute conventional thermally driven processes to realize small-scale, economically viable and environmentally friendly biorefineries. Gas discharge plasmas enable the conversion of renewable electric energy, supplied in the form of an electric field, to chemical energy through the formation of a highly reactive environment that can induce several transformations related to agricultural waste valorization processes. Herein, we review the application of plasma technology to lignocellulosic biomass upgrade, aiming to provide the scientific background and technical challenges in this rapidly emerging research field. To bridge the gap between plasma science and biomass valorization technologies, we initially present the technical aspects of plasma reactors related to biomass processing and further discuss the advances in plasma processing for each biomass conversion technology, providing insights into the related plasma chemistry and interaction mechanisms. Here, we first focus on the low and medium-temperature biomass conversion processes, including biomass pretreatment and delignification to promote enzyme or acid-catalyzed hydrolysis to sugars and biomass liquefaction using plasma electrolysis. Then we discuss the high and very high-temperature conversion processes, such as plasma-assisted pyrolysis and gasification to syngas and plasma application to tar removal, combustion, and vitrification. Overall, this review provides knowledge at the interface of plasma science and biomass conversion technology to promote the interaction between the individual communities, which is crucial for the further advancement of the field.
Devolatilization kinetics were determined using a modified micropyrolyzer reactor for several biomass feedstocks: switchgrass, corn stover, red oak, and pine. Here, the micropyrolyzer was directly coupled to a flame ionization detector (FID) to track the release of volatiles from the biomass. Time series data from these experiments was analyzed to determine apparent devolatilization rates. Care was taken to assure the experiments were isothermal and kinetically limited calculating a Biot number less than 0.1 and pyrolysis numbers greater than 10, which simplifies the derivation of devolatilization rates. A single, first order reaction was able to model devolatilization rates at temperatures up to 500 °C. No correlation was found between the inorganic content of the biomass and its rate of devolatilization. Apparent activation energies were in the range of 54.9–88.4 kJ mol –1 . The rate coefficient at 500 °C was calculated as 1.90–5.14 s –1 for the four feedstocks.
Consistent and reliable preprocessing, conveyance, and reactor in-feed systems, particularly for low-cost waste feedstocks, remains a major technical challenge for the emerging Bioeconomy. By identifying critical biomass attributes and connecting them to flow and conversion behavior, science-driven system designs can address these often-overlooked solids handling challenges. The Wonderful Company (TWC) is the world's largest almond and pistachio grower, generating 250,000 dry tons/year of waste material including hulls, shells, and wood (>5 million tons/year industry wide in the U.S.). This project seeks to turn this environmental and economic liability into a sustainable and profitable resource, targeting conversion via gasification to syngas for electricity and bio-char, by addressing related material handling and feeding challenges. Based on optimized preprocessing strategies, bulk material flow, and thermal conversion properties, an overall system design will be developed. The methodology will be tested with FCIC's benchmark loblolly pine residues, to demonstrate the robustness of the overall approach and provide insight and guidance for future systems. The project will culminate in extended field trials to demonstrate an improved continuous feeding system with a commercial biomass-to-electricity gasifier vendor, and an economic analysis demonstrating a reduction in electricity production costs by maximizing on-stream time while minimizing preprocessing and CapEx costs.
Ex situ catalytic fast pyrolysis (CFP) uses a secondary reactor to upgrade biomass pyrolysis vapors to stabilized CFP oils with reduced oxygen content. In one configuration, the secondary reactor is operated as a packed-bed swing reactor system which allows coke-deactivated beds to be decarbonized in situ while other beds remain online for vapor upgrading. In situ decarbonization must be done carefully to avoid irreversible deactivation and/or physical degradation of catalyst pellets. Given that packed bed reactors are well known to have poor heat transfer characteristics, this is a critical issue impacting scaleability and commercial viability of the technology. To predict thermal excursions during regeneration, finite element computational models have been built to assist in scaling up oxidative decarbonization of a Pt/TiO2 CFP catalyst (0.5 mm spheres) from a bench scale packed bed with 100 g of catalyst to a pilot scale packed bed with 2 kg of catalyst and internal cooling tubes. Based on transient measurements of outlet temperature and effluent CO2 concentration, and using an assumed coke profile and activation energy, this paper demonstrates that specific combinations of effective thermal conductivity and wall heat transfer coefficient can fit bench scale oxidative regeneration data equally well. For the upscaled 2 kg bed, four bench-scale “best fit” parameter pairs give different predictions for location and magnitude of thermal excursions, with the maximum computed bed temperature gradients ranging from 30 °C cm-1 to as high as 3000 °C cm-1. The larger the fraction of heat removal by conduction through the cooling tubes, the greater the differences between the parameter pairs. The modelling results presented in this paper cast doubt on the industrial viability of the proposed combination of catalyst, bed and regeneration process, and point to the need for alternate reactor designs. However, there is considerable uncertainly in some of the key model parameters. The reliability of model predictions can be increased by adding more temperature measurements at key bed locations, testing additional variations in process conditions, performing careful bed dissections to determine the true coke profile, and perhaps most importantly, directly measuring the effective thermal conductivity of the catalyst pellets.
Increasing concerns about global carbon emissions due to fossil fuel use has created interest in renewable fuel alternatives, such as lignocellulosic biomass. With an estimated global biomass production probability ten-fold higher than projected need, functionalizing and scaling biomass conversion processes, like pyrolysis, is a promising component of a diverse sustainable energy program (Kan, Strezov, & Evans, 2016). Pyrolysis reactors employed in biomass conversion often encounter the known problem of screw feeder plugging, halting work and reducing efficiency of biorefineries. Although the screw feeder is not heated directly, conductive heat transfer from the fluidized bed pyrolysis reactor creates a temperature gradient, where particles experience temperatures between 22°C and 500°C from the time they enter the feeder to being emptied into the reactor (Digman, Joo, & Kim, 2009; Nieminen & Folke, 1982). The impact of unintentional heating on this highly variable feedstock may result in particle morphology modification, surface texture transformation, and the evolution of viscous compounds and may contribute to screw feeder plugging (Haas, Nimlos, & Donohoe, 2009; Ingram et al., 2008). We hypothesized that particles of various anatomical fractions (including needles, branches, bark, cambium, and whitewood) will experience dramatic changes during this heating regime, which will be characterized by decreased particle size, increased surface roughness, degradation of key structural macromolecules, and generation of viscous compounds that would result in increased particle friction and cohesion, contributing to screw feeder plugging.
There is global interest in the conversion of biomass into sustainable low-carbon-footprint fuels and chemicals as an alternative to non-renewable fossil feedstocks. Feeding biomass solids into pressurized reactors is one of the key steps in biomass conversion. Predicting mechanical failure and energy requirements for this step helps avoid upstream processing bottlenecks and enables efficient operation of a biorefinery. Here, in this work, we developed a predictive computational model for biomass screw feeders that capture the highly viscous, non-Newtonian and compressible behavior of biomass slurries. Biomass compressible behavior is formulated by an equation of state and the non-Newtonian rheology is represented by a density-dependent viscosity model. Experimental data from two compression screw-feeder systems are presented as a validation for our model. Our model successfully predicted the location of the compressed biomass “plug”, biomass flow rate, and the required torque at different operating conditions for the experimental conditions studied in this work.
This project cultivated microalgae biomass as attached growth on a 3,000 gallon pilot Rotating Algae Biofilm Reactor to remediate municipal wastewater by removing nutrients nitrogen and phosphorus and also produce value bioproducts including compostable bioplastic.
Biomass pyrolysis is a technology that uses high temperatures to break down biomaterials like wood without completely burning them. Products include char, combustible gas, and vapors; the vapors can be condensed into a liquid with myriad uses. This chapter serves as a primer for the fundamental physics and chemistry involved in biomass pyrolysis, common reactor systems, and some reported uses for the products.
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The conversion of biomass feedstocks into fuels and chemicals using fast pyrolysis is a promising approach to renewable energy. Feed screws that convey biomass to pyrolysis reactors, however, often encounter plugging. Indirect heating of the feed screw occurs due to contact with the pyrolysis chamber, resulting in a heating gradient ranging from ambient temperature (22 °C) to reactor temperature (500 °C). Given that major cell wall macromolecules, such as lignin, cellulose, and hemicellulose, begin to produce bio-oils and volatile resin acid compounds within this temperature gradient, we hypothesized that indirect heating during feed screw conveyance is sufficient to cause premature degradation of biomass. We characterized this degradation by observing increases in surface roughness, changes in overall particle morphology, and the production and deposition of bio-oils on biomass particle surfaces. Correlative analysis between optical in situ hot-stage microscopy, confocal Raman spectroscopy, and SEM analysis revealed that heating at temperatures as low as 375 °C caused significant increases in surface roughness, with large fissures forming between and within cell walls. Additionally, droplets of bio-oil were observed on particles, especially in the bark and cambium samples. This work suggests that these phenomena contribute to particle agglomeration, leading to feed screw plugging, and that engineering a solution to cool the feed screw could prevent particle agglomeration and reduce plugging incidents, thereby increasing biomass processing efficiency.
Transitioning to a bioeconomy that makes use of low-emission and waste feedstocks requires greater flexibility to accommodate seasonal variations and mitigate long-term storage challenges, such as material loss and fire risk. To achieve this goal, biomass deconstruction technologies must efficiently handle diverse feedstocks. Here, we assess the cost of using butylaminea distillable solventto deconstruct 22 different biomass feedstocks: 7 herbaceous, 9 woody, 4 food processing residues, and 2 blends. Lignocellulosic sugar production costs, based on current empirical data, range from $1.3 to 6.1/kg, suggesting that substantial improvements are required to compete with conventional sugars. The high solvent loading (850 g/kg of whole slurry) is a process bottleneck. Lowering the solvent loading to 59 g/kg of whole slurry, demonstrated in an L-scale reactor using poplar biomass, reduces the minimum sugar selling price by 33%. Solvent loading and recovery, solid loading, sugar yield, enzyme use, and delivered biomass cost all play key roles in reaching sugar production costs of $0.45-0.79/kg. Strategic feedstock blending to maximize carbohydrate content, process optimization to improve conversion efficiency, and the selection of low-cost feedstocks are important to advancing feedstock-flexible biorefineries.
Compression feed screws are commonly used in biorefineries for the continuous feeding of biomass feedstock into reactors. Developing methods to assess the feasibility of feeding granular materials in a compression feed screw is critical for reducing solids handling issues during operation. A laboratory-scale compression feed screw has been built to measure critical process parameters of the feeding operation, namely the driving torque and the mass flow rate. The process parameters of two granular materials, microcrystalline cellulose Avicel PH-200 and milled corn stover are measured using the laboratory-scale feeder. The results show that a larger torque is required to feed corn stover than Avicel PH-200, even though the former consists of more compressible particles. Further, the device can capture real-time fluctuations in the process parameters during operation. Here, the laboratory-scale feeder can be used to compare the feeding of different granular materials and the measured parameters can be used to validate predictive models for a compression screw feeding process.
Firebrand burning is a complex phenomenon that is influenced by several parameters which are difficult to fully explore experimentally. Computational fluid dynamics models capable of predicting local quantities are essential for accurate prediction of char oxidation in firebrands. This article presents a computational fluid dynamics model to estimate firebrand mass loss, diameter change, and surface temperature during char oxidation. The model was validated using previously conducted wind tunnel experiments. These experiments were conducted for firebrands of two different aspect ratios, which were arranged in three different configurations (single, horizontal array, and vertical array), and for four different wind speeds (0.5, 1, 1.5, and 2 m/s). The computational fluid dynamics results were compared with a previous 1 D model. In all the test cases, the computational fluid dynamics model predicted the physical phenomena with significantly improved accuracy compared to a 1 D model. The char oxidation model presented in this article can be coupled with other models to study firebrand generation and trajectory, biomass pyrolysis, fluidized bed reactors, and coal combustion.
Fast pyrolysis is an intricate process due to the variability and anisotropy of lignocellulosic biomass and the complicated chemistry and physics during conversion in a bubbling fluidized bed reactor (BFBR). The complexity of biomass fast pyrolysis lends itself well to computational fluid dynamics (CFD) and discrete element (DEM) analysis, which promises to reduce experimental time and its associated cost. This work investigated switchgrass fast pyrolysis simulated by computational fluid dynamics coupled with a discrete element method to track individual reacting biomass particles throughout a bench-scale BFBR reactor. We accounted for the fast pyrolysis chemistry through a comprehensive reaction scheme with secondary cracking reactions. We performed a three-step reduction for secondary cracking reactions to convert the full cracking scheme into a reduced scheme easily incorporated into our model. We assessed the impact of operational conditions on the steady-state yields of liquid bio-oil, non-condensable gases (NCG), at 550 °C over a range of fluidization numbers (2 – 6 Umf), reported as a ratio to the minimum fluidization velocity (Umf). At steady-state, the volatile bio-oil yield had a range of 49.3–50.4 wt%. Levoglucosan was the primary volatile component present with 21 wt% of the bio-oil while water was the second largest with 20 wt%. The reduction of the secondary reaction schemes did not appreciably affect the overall yields of switchgrass pyrolysis compared to the full secondary scheme.
2024 AIChE Annual Meeting conference presentation detailing the planned Advanced Scale Up Reactor Experiment (ASURE) facility planned for construction on the NETL site in Morgantown, WV.