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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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A Machine Learning Model for Predicting Composition of Catalytic Coprocessing Products from Molecular Beam Mass Spectra

Demand for the development of an automated and integrated refining process for biofuels has increased in recent years due to the lack of generalized process inspection tools. In bio-oil upgrading processes, all process variables are maintained based on the offline specification of intermediates and products. A lack of real-time product specifications in batch-wise monitoring can cause process failure and wasted resources. Therefore, there is a need for a fast and accurate intermediates/product specification tool that can be used for real-time specification to reduce waste and mitigate the risk of process failure. Here, to address this gap, we developed a machine learning (ML) model for predicting speciated bio-oil composition, including paraffin, iso-paraffins, olefins, naphthene, and aromatics. The model is trained using the mass spectra from upgraded products collected in the vapor phase before condensation and predicts the composition of the condensed product. Training ML models using raw mass spectra is challenging due to numerous overlapped peaks originating from different parent compounds. With this in mind, we propose a protocol that (i) transforms raw mass spectra to chemistry-inspired predefined features and (ii) trains decision tree-based models using these features. Our results show that the random forest model was robust against overfitting and had the highest accuracy compared to other models. Moreover, a stochastic ablation method determined the eight most significant features while maximizing the accuracy. Our protocol facilitates real-time compositional analysis of upgraded bio-oils and thus real-time process monitoring. Additionally, this protocol enables the rational design of efficient catalysts and the determination of optimal process conditions.

09 BIOMASS FUELS↗

Coprocessing Biomass Fast Pyrolysis and Catalytic Fast Pyrolysis Oils with Vacuum Gas Oil in Refinery Hydroprocessing

Fast pyrolysis and catalytic fast pyrolysis (CFP) have been considered to be promising approaches for converting lignocellulosic biomass into liquid bio-oils followed by upgrading to produce fuel-range hydrocarbon products. Co-processing fast pyrolysis and CFP bio-oils with petroleum feedstocks leverages the existing petroleum refining infrastructure, which reduces Capex for the overall conversion technologies for biomass to fuel and enables fast adoption of the technologies and biofuels. Here, we reported the co-processing of different woody fast pyrolysis and CFP bio-oils with petroleum vacuum gas oil (VGO) at 5-25% bio-oil blending levels over a NiMo sulfide catalyst for mild hydrocracking. The catalyst activities over ~300 hours time on stream, the product yield and properties, and the biogenic carbon content in products are provided. Co-processing of the raw fast pyrolysis bio-oil in our configuration was not successful because the instability of the bio-oil resulted in reactor plugging and bio-oil stabilization by hydrogenation enabled their stable co-processing with VGO, whereas the CFP bio-oil can be co-processed without pretreatment. Simultaneous hydrodesulfurization, hydrodeoxygenation, and hydrocracking reactions occurred during co-processing and no obvious decrease in hydrodesulfurization and hydrocracking conversion of VGO was observed, suggesting the minimal impact of co-processed bio-oils on the reaction of VGO and also the simultaneous conversion of bio-oil and VGO to produce fuel products with much-reduced S and O content. Biogenic carbon content in co-processed products calculated by yield mass balance, together with results from isotopic measurements, indicates high biogenic carbon incorporation into liquid hydrocarbon products. In conclusion, higher biogenic carbon incorporation into fuel products was observed when co-processing CFP bio-oils than the fast pyrolysis bio-oils and over 90% of carbon in CFP bio-oil was incorporated into liquid hydrocarbon products.

09 BIOMASS FUELS↗

R&D with NREL's Davison Circulating Riser System

The Davison circulating riser (DCR) is the National Renewable Energy Laboratory's (NREL's) pilot-scale recirculating riser reactor system. Coupled with an upstream fluid-bed pyrolysis system, it permits evaluation of catalytic cracking of biogenic feedstocks, as well as coprocessing of biogenic and fossil feedstocks in a commercially relevant pilot fluid catalytic cracker.

09 BIOMASS FUELS↗

Catalytic Fast Pyrolysis Oil Stand-Alone and Co-Hydroprocessing Case Studies: Design, Cost, and Sustainability Based on Process Model Predictions

Refined liquid fuels provide conveniences for road, rail, air, and marine transportation due to high energy density, ease of transport and storage, and existing production and distribution infrastructure. Biomass conversion technologies can help diversify and increase the supply of liquid fuels towards a more robust energy future. The backbone of such development must include reliable, high-volume biomass supply chains and efficient utilization of those resources. These activities, if pursued, will lead to rural infrastructure development and new jobs.

09 BIOMASS FUELS↗

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↗

Pyrolysis Vapor and Bio-Oil Preconditioning via Ex Situ Hydrodeoxygenation and Alkylation Using a Heteropolyacid Catalyst

Ex situ catalytic preconditioning of biomass pyrolysis vapors (partial deoxygenation) has the potential for both reducing the oxygen content and beneficially influencing the oxygen speciation of condense bio-oils for enhancement of downstream condensed phase upgrading processes. Here, condensed phase upgrading processes may refer to both coprocessing and hydroprocessing with vacuum gas-oil (VGO). Reduction of oxygen content to produce bio-oils with greater hydrophobicity can enhance VGO-solubility while tailoring of oxygen speciation by removal of reactive carbonyls (e.g., acetic acid) can lessen catalytic deactivation via coking reactions. 1,2 Furthermore, enhanced VGO-solubility and reduced coking leads to greater biogenic carbon incorporation in end-products from condensed phase upgrading processes. By leveraging the hydrodeoxygenation and alkylation activity of a titania-supported molybdenum-heteropolyacid (Mo-HPA/TiO2) catalyst, pyrolysis vapors and resulting condensed bio-oils were effectively preconditioned for downstream upgrading. 3 Data regarding the use of Mo-HPA/TiO2 for pyrolysis vapor preconditioning will be presented on, including method of employment, catalyst characterization, and impacts on bio-oil in relation to downstream condensed phase upgrading processes. Our approach is to: Compare Mo-HPA/TiO2 product distribution to HZSM-5; Investigate Mo-HPA/TiO2 regeneration and characterize changes in acid site character; Assess product differences in terms of enhanced VGO-solubility.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Model quantification of the effect of coproducts and refinery co-hydrotreating on the economics and greenhouse gas emissions of a conceptual biomass catalytic fast pyrolysis process

Here we present model results for a scaled-up conceptual process informed by bench scale biomass catalytic fast pyrolysis (CFP) and hydrotreating experimental data. This process uses a Pt/TiO 2 catalyst during CFP, which produces a partially deoxygenated organic biocrude intermediate that is then hydroprocessed to a hydrocarbon fuel blendstock; the catalyst also enables high yields of acetone and methyl-ethyl-ketone (MEK) coproducts. Two options for hydroprocessing were modeled: (A) co-hydrotreating at a petroleum refinery using hydrogen sourced from steam reforming of natural gas and (B) standalone hydrotreating at a biorefinery using hydrogen sourced from CFP off gases. The results revealed that Case A was economically advantageous with a modeled minimum fuel selling price (MFSP) of $\$$2.83/GGE or gallon gasoline equivalent (in 2016 US dollars), while the additional cost of standalone hydrotreating facilities in Case B increased the MFSP to $3.13/GGE. Conversely, greenhouse gas (GHG) emissions were lower for Case B (3.9 g CO 2 e/MJ) compared to Case A (21.5 g CO 2 e/MJ) due to the use of biogenic (Case B) and fossil-derived (Case A) hydrogen. In a third option (Case C), the requirements for separation and purification of acetone and MEK were removed from the refinery co-processing scenario (Case A) to evaluate the impacts of this process simplification. Elimination of these coproducts increased the MFSP to $3.21/GGE and GHG emissions to 35 g CO 2 e/MJ. These comparisons based on our detailed conceptual models provide economic and sustainability guidance regarding processing choices for future biorefineries. While refinery coprocessing using existing equipment and the production of relatively valuable coproducts can benefit the economics, the hydrogen-source and biogenic coproducts can have significant impacts on the sustainability of the process, and feasibility to use CFP off-gases or other renewable sources for hydrogen production can help lower GHG emissions.

09 BIOMASS FUELS↗

Co-processing Part 3: LANL Studies Quicker Method to Identify Renewable Carbon Percentages in Fuel Blends [Success Story]

Upgrading bio-oils with petroleum feedstocks at existing refineries—known as “co-processing”—could offer a fast pathway for lowering the carbon footprint of today’s transportation fuels. With equipment and infrastructure already in place, more than 100 refineries across the country are equipped to integrate bio-oil into their processes. But just where might companies insert sustainable bio-oils into existing refinery systems like fluid catalytic crackers and hydrotreaters? If successful, just how much of that renewable or “green” carbon makes it into final fuel products? In this three-part blog series, the National Renewable Energy Laboratory (NREL), Pacific Northwest National Laboratory (PNNL), and Los Alamos National Laboratory (LANL) offer insights into these pressing coprocessing questions—and others—amid the push to dramatically expand the production of climate-friendly fuels. Read part 1 and part 2.

02 PETROLEUM↗

Opportunity Assessment for Sustainable Aviation Fuel Production from Woody Biomass via Ex Situ Catalytic Fast Pyrolysis and Refinery Hydroprocessing

Biofuels have become a promising solution to reduce emissions in hard-to-electrify transportation sectors, such as aviation. However, several biofuel conversion pathways will likely be needed to scale sustainable aviation fuel (SAF) production to meet lower carbon intensity goals when biomass feedstock availability constraints are considered. This study evaluates the future potential of the catalytic fast pyrolysis (CFP) pathway to contribute to U.S. SAF production goals as outlined in the U.S. Department of Energy’s (DOE) SAF Grand Challenge, understanding that the CFP pathway is still under development toward maturity and scaleup. National forestland resource data from the DOE’s 2023 Billion Ton Study are integrated with recent experimental results demonstrating end-to-end woody biomass conversion to SAF via CFP and hydroprocessing in a novel bioeconomy optimization framework. U.S. refinery hydroprocessing capacity is also considered with repurposing and coprocessing strategies. Results indicate that the CFP process can contribute up to 4.6 billion gallons of SAF annually by 2040, meeting 13% of the 2050 SAF Grand Challenge target while reducing the carbon intensity (CI) of the U.S. jet fuel pool by 16%. The study further explores optimal processing strategies, suggesting that colocating CFP operations with existing petroleum refineries and repurposing some U.S. hydrocracking capacity may offer significant cost advantages and enhance the commercial viability of the CFP pathway. These results underscore the CFP pathway’s potential to support the global aviation industry’s lower carbon intensity objectives while producing other renewable fuels and products.

09 BIOMASS FUELS↗