Multiphase Flow Equations for Modeling Tar Production from Biomass Particle Pyrolysis in a Fluidized Bed Reactor
A general model is presented for mathematically describing the physics and chemistry of biomass pyrolysis in a fluidized bed reactor.
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A general model is presented for mathematically describing the physics and chemistry of biomass pyrolysis in a fluidized bed reactor.
A novel multiphase flow model is presented for describing the pyrolysis of biomass in a bubbling fluidized bed reactor. The mixture to biomass and sand in a gaseous flow is conceptualized as a particulate phase composed of two classes interacting with the carrier gaseous flow.
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Open microalgal ponds used in industrial biomass production are susceptible to a number of biotic and abiotic environmental stressors (e.g., grazers, pathogens, pH, temperature, etc.) resulting in pond crashes with high economic costs. Identification of signature chemicals to aid in rapid, non-invasive, and accurate identification of the stressors would facilitate targeted and effective treatment to save the algal crop from a catastrophic crash. Specifically, we were interested in identifying volatile organic compounds (VOCs) that can be used to as an early diagnostic for algal crop damage. Cultures of Microchloropsis gaditana were subjected to two forms of algal crop damage: (1) active grazing by the marine rotifer, Brachionus plicatilis, or (2) repeated freeze–thaw cycles. VOCs emitted above the headspace of these algal cultures were collected using fieldable solid phase microextraction (SPME) fibers. An untargeted analysis and identification of VOCs was conducted using gas chromatography-mass spectrometry (GC-MS). Diagnostic VOCs unique to each algal crop damage mechanism were identified. Active rotifer grazing of M. gaditana was characterized by the appearance of carotenoid degradation products, including β-cyclocitral and various alkenes. Freeze–thaw algae produced a different set of VOCs, including palmitoleic acid. Both rotifer grazing and freeze–thawed algae produced β-ionone as a VOC, possibly suggesting a common stress-induced cellular mechanism. Importantly, these identified VOCs were all absent from healthy algal cultures of M. gaditana. Early detection of biotic or abiotic environmental stressors will facilitate early diagnosis and application of targeted treatments to prevent algal pond crashes. Thus, our work further supports the use of VOCs for monitoring the health of algal ponds to ultimately enhance algal crop yields for production of biofuel.
Microalgae are an efficient platform for the sustainable production of foods, fuels, and bioproducts. Due to the vast natural diversity of microalgae, choosing an ideal species for production can be challenging, and laboratory-derived productivity data may be misleading. In the present study, nine species of green algae (Chlorophyta) were isolated directly from an outdoor pilot production facility, identified via sequencing and microscopy, cultured under standard laboratory conditions to assess lipid content, and then cultivated in 80-L cultures in a greenhouse over the course of a year to assess productivity. Analysis of lipid content from laboratory-grown cultures revealed that these strains had high concentrations of C16 and C18 fatty acids and lipid content not exceeding 30% of dry weight during growth phase. In the greenhouse, Parachlorella kessleri-SD23 had the highest annual productivity, yielding an annual average of approximately 19 g/m 2 /d and 88 mg/L/d of biomass productivity. Furthermore, P. kessleri-SD23 had a total lipid content equal to about 19% of dry weight during growth phase under laboratory conditions with the highest concentration of C18:2 and C18:3 fatty acids among the isolates.
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.
The design of the facility is described in terms of its use as an investigation tool for evaluating crop growth in space with reference to required emerging technologies. NASA's CELSS Test Facility (CTF) is designed to permit the measurement of crop-plant productivity under microgravity conditions including biomass production, food production, water transpiration, and O2/CO2 exchanges. Crucial hardware tests and qualifications are identified to assure the operation of CTF technologies in space including the nutrient-delivery, water-condensation, and gas-liquid-mixing subsystems. The design concept and related scientific requirements are described and shown to provide microgravity crop research. The CTF is expected to provide data for plant research and for concepts for bioregenerative life-support systems for applications to Martian, lunar, and space-station missions.
Recent techno-economic analysis (TEA) has underscored that for algal biofuels to be cost competitive with petroleum fuels, co-products are necessary to offset the cost of fuel production. The co-product suite must scale with fuel production while also maximizing value from the non-fuel precursor components. The co-product suite also depends on algal biomass composition, which is highly dynamic and depends on environmental conditions during cultivation. Intentional shifts in composition during cultivation are often associated with reduced biomass productivity, which can increase feedstock production costs for the algae-based biorefinery. The optimal algae-based biorefinery configuration is thus a function of many factors. We have found that comprehensive TEA, which requires the construction of process models with detailed mass and energy balances, along with a complete accounting of capital and operating expenditures for a commercial-scale production facility, provides invaluable insight into the viability of a proposed biorefinery configuration. This insight is reflected in improved viability for one biorefining approach that we have developed over the last 10 years, namely, the Combined Algal Processing (CAP) approach. This approach fractionates algal biomass into carbohydrate-, lipid-, and protein-rich fractions, and tailors upgrading chemistry to the composition of each fraction. In particular, transitioning from valorization of only the lipids to a co-product suite from multiple components of high-carbohydrate algal biomass can reduce the minimum fuel selling price (MFSP) from more than $8/gallon of gasoline equivalent (GGE) to $2.50/GGE. This paper summarizes that progress and discusses several surprising implications in this optimization approach.
The composition of algal biomass is highly dynamic, with protein, lipid, and carbohydrate contents varying in response to nutrient and environmental conditions during cultivation. Because shifts in biomass composition are often associated with reduced biomass productivity, production costs can often increase if targeting higher biomass compositional quality (enriched in carbohydrates or lipids at reduced protein content) as input for the algal biorefinery. The optimal algal biorefinery configuration is thus a function of many factors. One of the key strengths of the Combined Algal Processing (CAP) process is the versatility of feedstocks and products produced. The concept has been demonstrated with ethanol and a variety of carboxylic acids (succinic, butyric, muconic) as coproducts along with lipid upgrading to biofuel. Modification of the approaches, processes and downstream upgrading to fuels has allowed the CAP process to reduce costs and improve efficiency. Muconic acid is a high-value, potential fermentation coproduct of interest because it can be easily converted to adipic acid, a high-volume monomer for the production of nylon and other valuable consumer plastics. As such, the production of muconic acid through CAP was explored to expand the suite of products from algal biomass and to begin exploring the valorization of high protein content biomass from rapidly grown algae biomass. We have established initial performance parameters and shown that the range of substrates consumed by the muconic acid-producing microbe, Pseudomonas putida, includes at least glucose, mannose, glycerol, and lactic acid. We achieved complete utilization of these four major hydrolysate substrates achieving productivities of 0.037 (g/L/h) from Scenedesmus obliquus and 0.029 (g/L/h) from Monoraphidium minutum hydrolysates. Final titer and process yield (mol of muconic acid per mol of substrate (molP/molS)) were 0.99 g/L and 0.42 molP/molS from S. obliquus hydrolysate and 0.75 g/L and 0.23 molP/molS from M. minutum hydrolysate, respectively.
Abstract Background Switchgrass ( Panicum virgatum L.), a North American prairie grassland species, is a potential lignocellulosic biofuel feedstock owing to its wide adaptability and biomass production. Production and genetic manipulation of switchgrass should be useful to improve its biomass composition and production for bioenergy applications. The goal of this project was to develop a high-throughput stable switchgrass transformation method using Agrobacterium tumefaciens with subsequent plant regeneration. Results Regenerable embryogenic cell suspension cultures were established from friable type II callus-derived inflorescences using two genotypes selected from the synthetic switchgrass variety ‘Performer’ tissue culture lines 32 and 605. The cell suspension cultures were composed of a heterogeneous fine mixture culture of single cells and aggregates. Agrobacterium tumefaciens strain GV3101 was optimum to transfer into cells the pANIC-10A vector with a hygromycin-selectable marker gene and a pporRFP orange fluorescent protein marker gene at an 85% transformation efficiency. Liquid cultures gave rise to embryogenic callus and then shoots, of which up to 94% formed roots. The resulting transgenic plants were phenotypically indistinguishable from the non-transgenic parent lines. Conclusion The new cell suspension-based protocol enables high-throughput Agrobacterium -mediated transformation and regeneration of switchgrass in which plants are recovered within 6–7 months from culture establishment.
Plastic production from fossil feedstocks (e.g., naphtha, coal, and natural gas) is not sustainable and causes known environmental impacts such as global warming. A possible solution is to shift production pathways to use biomass, which is a sustainable feedstock that can sequester atmospheric carbon dioxide. This study presents an optimization-based pathway analysis framework for evaluating the carbon footprints of the production of mainstream plastics from biomass and fossil feedstocks. We use the modeling framework to quickly navigate complex interdependencies that exist between the production pathways of different plastics and to determine pathways of minimum production cost under a range of carbon pricing scenarios. The framework interprets carbon prices as an exogenous taxation scheme or an endogenous negative value perceived by producers. The proposed approach reveals the biomass feedstock quantities needed to displace fossil counterparts and the plastics and technologies that should be prioritized. The framework can also be used for evaluating system-wide trade-offs between production costs and carbon footprints that arise from pathway interdependencies. We also evaluate hidden environmental impacts associated with the large-scale use of biomass as a feedstock, such as land use and water eutrophication that results from a significant increase in fertilizer use. Therefore, it is important to highlight that there are trade-offs between decarbonization and other environmental issues. Here, the proposed framework provides an integrative platform for basic techno-economic and life-cycle data that can be used for analyzing diverse scenarios and determining necessary technology targets (e.g., yields, footprints, and costs) to achieve required levels of decarbonization.
The Picochlorum genus is a distinctive eukaryotic green-algal clade that is the focus of several current biotechnological studies. It is capable of extremely rapid growth rates and has exceptional tolerances to high salinity, intense light, and elevated temperatures. Importantly, it has robust stability and high-biomass productivities in outdoor field trials in seawater. These features have propelled Picochlorum into the spotlight as a promising model for both fundamental and biotechnological research. Recently, several genetic tools, including genome editing, were developed for these algae, enabling insights into Picochlorum photophysiology and algal transformations for expanded capabilities. Here, we survey the Picochlorum genus, its genetic toolbox, recently characterized transformants, and discuss the commercial potential of Picochlorum as a salt-water photoautotrophic biocatalyst.
The economic success of biofuels and bioproducts depends on system-level optimization including biomass production and conversion. Hydrothermal liquefaction (HTL) can convert wet biomass such as microalgae into a biofuel intermediate (BFI) under elevated temperatures and pressure. An understanding of the impacts of biomass composition on BFI yield and quality can inform genetic engineering strategies in the improvement of biochemical composition for biofuel production. In this work, wild type cyanobacterium Synechocystis sp. PCC 6803 biomass was doped with various common cellular storage compounds in lab-scale HTL experiments. Doping with glycogen or polyhydroxybutyrate (PHB) significantly reduced BFI yields, while doping with triglycerides (TAG) or medium chain-length polyhydroxyalkanoate (mcl-PHA) increased BFI yield and quality. In light of these observations, a genetically engineered Synechocystis strain deficient in glycogen biosynthesis was cultivated to produce biomass for HTL, leading to a 17% increase in BFI yield. In addition, we built a multiphase component additivity (MCA) model that can predict BFI yield and quality with PHAs in the biomass. This work demonstrates an effective strategy to integrate strain development with downstream biomass conversion to maximize biofuel yield, with lessons applicable to microalgae as well as other biomass.
The U.S. Department of Energy promotes production of advanced liquid transportation fuels from lignocellulosic biomass by funding fundamental and applied research that advances the state of technology (SOT). As part of its involvement in this mission, Idaho National Laboratory completes an annual SOT report for nth-plant and 1st-plant herbaceous biomass feedstock logistics. The purpose of the SOT is to provide the status of feedstock supply system technology development for herbaceous biomass to biofuels relative to technical targets and cost goals from specific design cases, based on data and experimental results. Although conventional feedstock supply systems form the backbone of the emerging biofuels industry, they have limitations that restrict widespread implementation on a national scale. To meet the demands of the future industry, the feedstock supply system must shift from the conventional system to what has been termed “advanced” supply systems. In advanced designs, a distributed network of aggregation and processing centers, termed “depots,” are employed near the points of biomass production (i.e., the field or forest) to reduce feedstock variability and produce feedstocks of a uniform format, moving toward biomass commoditization. The 2022 Herbaceous SOT is part of a vision of achieving an implemented advanced feedstock supply system, which produces a stable, tradable commodity at the decentralized distributed depot. It utilizes feedstock fractionation by incorporating technologies that can separate the biomass into its anatomical fractions (leaves, husks, stems and cobs) to reduce impurities and produce fractions that satisfy downstream quality considerations. By using a series of air classification steps, this strategy can reduce the extrinsic ash in corn stover and produce enriched tissue fractions that can be blended to a conversion specification or converted individually in optimized biochemical conversion campaigns. Additionally, a majority of the leaves (which do not meet the quality specification) are separated out early and can be supplied to alternate markets. The 2022 Herbaceous SOT incorporates an advanced biomass fractionation and processing system to produce pellets enriched tissues from three-pass corn stover. The resulting enriched pellets are delivered to the biorefinery individually where they can be blended to a specification or converted in campaigns where the conditions are optimized for each tissue. Unused fractions can be sent to a a midstream market or to a different conversion process that is better suited to their properties to offset the cost of the delivered feedstock. The main benefits from the proposed system can be summarized as: (1) $6.86/dry ton (2016$) lower cost for the air classification due to elimination of the requirement to discard the high ash lights fraction; (2) $1.56/dry ton lower delivered cost by selling the unsuitable leaf fraction into the feed market as a midstream co-product (assuming a selling price that is 11% higher than their cost of production); (3) 0.98% increase in carbohydrate content (from 60.16% to 61.14%); and (4) 0.97% decrease in ash content (from 6.00% to 5.03%) compared to the 2021 Herbaceous SOT. Overall, the 2022 nth-plant Herbaceous SOT predicts a modeled delivered feedstock cost of $78.64/dry ton (2016$) if it is assumed that the enriched leaf fraction is sold at its production cost; this is a slight increase of $0.43/dry ton increase from the 2021 Herbaceous SOT nth-Supply case cost. The increased cost derived from a $0.38/dry ton increase in transportation and handling cost to procure more biomass (to replace the enriched leaf fraction that was not delivered to the biorefinery. The total preprocessing cost was $0.27/dry ton higher than the 2021 result because of updates to energy consumption, purchasing price and dry matter loss data for the rotary shear ($3.00/dry ton increase) and the pelleting mill ($4.52/dry ton increase). The data utilized were generated in pilot-scale tests in the Biomass Feedstock National User Facility (BFNUF) at INL and at Forest Concepts, including tests for rotary shear and pelleting of the air classified fractions. A greenhouse gas emissions analysis was performed by Argonne National Laboratory using the most up to date version of the Greenhouse Gases, Regulated Emissions, and Energy use in Transportation model (GREET®). The analysis showed an increase of 17.34 kg CO2e/dry ton from the 2021 SOT (67.71 kg CO2e/ton in the 2021 Herbaceous SOT to 85.05 kg CO2e/ton in the 2022 Herbaceous SOT). The net increase is primarily attributed to increased energy consumption in pelleting mill.
Abstract Enhancement of net primary production (NPP) in forests as atmospheric [CO 2 ] increases is likely limited by the availability of other growth resources. The Duke Free Air CO 2 Enrichment (FACE) experiment was located on a moderate‐fertility site in the southeastern US, in a loblolly pine ( Pinus taeda L.) plantation with broadleaved species growing mostly in mid‐canopy and understory. Duke FACE ran from 1994 to 2010 and combined elevated [CO 2 ] (eCO 2 ) with nitrogen (N) additions. We assessed the spatial and temporal variation of NPP response using a dataset that includes previously unpublished data from 6 years of the replicated CO 2 × N experiment and extends to 2 years beyond the termination of enrichment. Averaged over time (1997–2010), NPP of pine and broadleaved species were 38% and 52% higher under eCO 2 compared to ambient conditions. Furthermore, there was no evidence of a decline in enhancement over time in any plot regardless of its native site quality. The relation between spatial variation in the response and native site quality was suggested but inconclusive. Nitrogen amendments under eCO 2 , in turn, resulted in an additional 11% increase in pine NPP. For pine, the eCO 2 ‐induced increase in NPP was similar above‐ and belowground and was driven by both increased leaf area index ( L ) and production efficiency (PE = NPP/ L ). For broadleaved species, coarse‐root biomass production was more than 200% higher under eCO 2 and accounted for the entire production response, driven by increased PE. Notably, the fraction of annual NPP retained in total living biomass was higher under eCO 2 , reflecting a slight shift in allocation fraction to woody mass and a lower mortality rate. Our findings also imply that tree growth may not have been only N‐limited, but perhaps constrained by the availability of other nutrients. The observed sustained NPP enhancement, even without N‐additions, demonstrates no progressive N limitation.
The production of fuels from lignocellulosic biomass is key to reduce our reliance on petroleum and to promote a sustainable bioeconomy. Butyric acid (BA) is a promising chemical precursor for the production of renewable diesel and jet fuels. BA can be biologically produced from lignocellulosic sugars. However, challenges associated with product selectivity and recovery must be overcome to achieve industrially relevant metrics. Here, we evaluate various fermentation configurations and demonstrate near-homo-butyrate production by using the biocatalyst Clostridium tyrobutyricum. We also develop an advanced in situ product recovery process based on hybrid extraction-distillation (HED-ISPR) and conduct techno-economic analyses and life cycle assessments. We demonstrate that the HED-ISPR process lowers the overall capital and operating expenses and environmental impact compared to other traditional fermentation processes. Overall, BA minimum product selling price from biomass is 55% of the current BA selling price from petroleum, a significant decrease toward viable renewable fuel production.
A preliminary techno-economic analysis (TEA) was developed for the fiscal year (FY) 2022 state of technology (SOT) assessment to evaluate the benefits and risks of using demonstrated, high-productivity algae strains for fuels generation, including sustainable aviation fuel (SAF). In 2022, the marine algal strain, Picochlorum celeri, which demonstrated the highest outdoor biomass productivities reported to date in the DOE-funded open-pond raceway testbed at the Arizona Center for Algae Technology and Innovation (AzCATI), was tested for continuous hydrothermal liquefaction (HTL) processing at PNNL. HTL testing results demonstrated a biocrude yield of 0.33 g/g algae on an ash-free dry weight (AFDW) basis from P. celeri. The hydrotreatment testing of the HTL biocrude from P. celeri was also conducted to investigate the production of jet fuel from marine algal biomass. To the best of our knowledge, this is the first report of jet fuel production from autotrophically grown marine algal biomass. The current hydrotreating testing demonstrated approximately 22.7 wt% of the hydrotreated oil within the typical boiling-point range of jet fuel (150–250 °C). Initial testing of the jet fuel cut (JFC) showed that the physical properties under investigation were within typical ranges for petroleum-based jet fuels. The experimental work of this study closes the gap between outdoor algae cultivation and algae conversion to critical transportation fuels using the same algae strain for both cultivation and conversion testing. The continuous HTL and the upgrading testing described herein demonstrate the potential of producing sustainable aviation fuel (SAF) from algae cultivated in open-pond systems using the primary inputs of sunlight and carbon dioxide.