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At least 109 records · Page 6

A Review: Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing. and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and carbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes.

McCoy, LaShelle E.↗

Anaerobic Digestion of Food Waste: Products and Their Uses

This brochure provides a brief summary of products associated with anaerobic digestion of food waste, namely biogas and digestate. The focus is primarily on digestate and its utilization options, which include land application, direct and indirect fuel, bio-oil, biochar, and syngas, as well as other uses.

BIOMASS FUELS↗

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Thermochemical conversion of biomass to produce drop-in quality biofuels typically involves hydrodeoxygenation (HDO) steps following catalytic fast pyrolysis (CFP) to remove excess oxygen and create a more stable bio-oil product. HDO involves co-feeding the CFP vapor-phase product and H2 gas over a bi-functional catalyst. Reducible metal oxide-supported noble-metal catalysts (e.g., Pt/TiO2) are promising materials for HDO chemistry, with recent work aiming to elucidate the role of various Pt/TiO2 actives sites (i.e., Pt-metal, TiO2-support, Pt-TiO2-interfacial sites) in the competing desired deoxygenation and undesired decarboxylation/decarbonylation reactions for important classes of CFP vapor model compounds. Carboxylic acids are one important class of bio-derived compounds that has not been studied extensively for HDO on Pt/TiO2, particularly at the atomic level. Past experimental work evaluating Pt/C and Pt/TiO2 catalysts for acetic acid HDO (AA-HDO) demonstrated selectivity toward C-C and C-O bond-dissociation products, respectively. This work utilizes atomic-scale modeling to discern the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in AA-HDO. Using Pt(111) and Pt-TiO2-interface surface models, adsorption and reaction energetics calculated by density functional theory provide fundamental insights into the role of interfacial sites and oxygen vacancies in promoting desired deoxygenation pathways over undesired decarboxylation/decarbonylation pathways.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Determining the Role of Synthesis and Reaction Conditions on the Exposed Surface and Shape of ..beta..-Mo2C Catalysts

The production of drop-in quality biofuels typically can be achieved through catalytic fast pyrolysis (CFP) of biomass, followed by hydrodeoxygenation (HDO) of the vapor-phase product to reduce the oxygen content and stabilize the bio-oil product. To favor selectivity toward desired deoxygenation products, bifunctional catalysts with both acidic and hydrogenation sites are often employed. Due to both its oxophilicity and its ability to promote hydrogenation reactions, molybdenum carbide catalysts have shown promise for promoting the HDO of CFP vapors. However, the surface structure and composition of carbide catalyst particles are not well understood, precluding the establishment of fundamental structure-function relationships needed for the rational development of molybdedum carbide for HDO, as well as other reactions. For orthorhombic ..beta..-Mo2C, the (100) facet is largely studied for computational surface-reaction analyses, possibly due to its similarities with the close-packed (111) facet of noble-metal catalysts. However, it has previously been postulated through ab initio thermodynamic studies that the (111), (110), and (011) facets are most stable, though there is no consensus. Furthermore, while a majority of previous surface stability analyses of ..beta..-Mo2C focus on bulk terminations, the highly carburizing synthesis conditions and the use of ..beta..-Mo2C in carbon-containing reaction applications could introduce non-stoichiometric coverages of surface carbon. As such, this study uses ab initio thermodynamics calculations to assess the relative surface stability of the low-index facets of ..beta..-Mo2C, including consideration of varying the coverage of surface carbon. From this information, Wulff constructions are utilized to predict the synthesis and reaction condition-dependent shape and surface carbon composition of ..beta..-Mo2C catalyst particles.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Assessing the Role of the Support in Acetic Acid Hydrodeoxygenation Selectivity on Pt/TiO2

To produce drop-in quality biofuels following the thermochemical conversion of biomass via catalytic fast pyrolysis (CFP), hydrodeoxygenation (HDO) reactions can be performed to remove excess oxygen and create a more stable bio-oil product. HDO reactions involve co-feeding the CFP vapor-phase product and H2 gas over bi-functional catalysts, such as noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2). Recent model-compound studies, focusing on important classes of species in the CFP vapor mixture, have sought to determine the role of the various Pt/TiO2 actives sites (i.e., Pt-metal, TiO2-support, Pt-TiO2-interfacial sites) in producing the observed desired deoxygenation and undesired decarboxylation/decarbonylation products. One important class of compounds in the CFP vapor-phase product is carboxylic acids (e.g., acetic acid). Prior experimental work on acetic acid HDO (AA-HDO) found that Pt/C and Pt/TiO2 catalysts favored the formation of undesired C-C and desired C-O bond-dissociation products; however, the fundamental surface chemistry driving this shift in selectivity has not been established. This presentation employs atomic-scale modeling to determine, through comparisons of adsorption and reaction energetics, how Pt-metal, Pt-TiO2-interface, and interfacial-vacancy sites catalyze the competing reaction pathways for AA-HDO. Our analysis indicates that hydroxyl vacancies at the Pt-TiO2 interface are critical for lowering barriers for C-O bond-cleavage steps, such that they become favorable/competitive with respect to C-C bond-dissociation steps.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Co-Hydrotreating of Catalytic Fast Pyrolysis Oils with Straight-Run Diesel

Catalytic Fast Pyrolysis (CFP) of biomass provides an opportunity for producing stabilized bio-oils (CFP oils) that can be further processed into hydrocarbon transportation fuels via hydroprocessing. Standalone hydrotreating of CFP oils has been pursued and has been shown to be able to produce hydrocarbon products with low oxygen contents of <1wt%, but the process is costly due to the high requirements of hydrogen and high capital costs. The costs can be reduced by co-processing in refineries, which takes advantage of the existing refinery infrastructure and the economies of the larger scale of petroleum processing operations. In this contribution, we evaluated co-hydrotreating of CFP oil with straight-run diesel in a laboratory continuous hydrotreating reactor. The CFP oil had been produced over a bi-functional metal-acid catalyst (Pt/TiO2) and contained 17 wt% oxygen on dry basis, and it was fed to the reactor together with straight-run diesel in the proportion of 20 vol%:80 vol%. The co-hydrotreated diesel products had acceptable cetane numbers (>40), and the calculated carbon efficiencies were high (~95%) for the CFP portion of the feed mixtures. Biogenic carbon incorporation in the product was confirmed by C-14 analysis. Sulfided NiMo catalyst gave better performance with respect to the diesel product quality than CoMo did due to the higher hydrogenation activity of NiMo. A comparison of standalone hydrotreating of the CFP oil and the straight-run diesel to co-hydrotreating showed good correspondence. Major challenges and risks associated with co-hydrotreating are discussed in this presentation.

biomass↗

MSW Variability Mapping and Conversion to Biofuel

MSW (Municipal Solid Waste) is a form of biomass which consists of categorized components of waste/trash. The general categories are paper, yard trash, construction & debris, appliances, tires, glass, metals, aluminum & steel cans, plastics, organics, inorganics, and HHW (Household Hazardous Waste). This project focuses on the factors within a region or population that contribute to variability in the composition of MSW and in turn MSW’s convertibility to biofuel. A list of contributors was determined (Social Vulnerability Index, Access to Public Transportation, Racial Distribution, GDP, Personal Income) and then JMP was used to perform a Multivariate analysis to determine correlations and a Partial Least-Squares regression to determine Variable Importance Plots for each MSW category. In addition to data analysis, the convertibility of MSW to biofuel was studied via microwave pyrolysis system in order to separate and characterize the various gaseous and bio-oil products.

09 BIOMASS FUELS↗

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Thermochemical conversion of biomass to produce drop-in quality biofuels typically involves hydrodeoxygenation (HDO) steps following catalytic fast pyrolysis (CFP) to remove excess oxygen and create a more-stable bio-oil product. HDO reactions are performed by co-feeding the CFP vapor-phase product and H2 gas over a bi-functional catalyst. Noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2) are active and selective toward these HDO reactions. Griffin and co-workers showed that Pt/TiO2 catalysts promote the desired deoxygenation steps for m-cresol HDO while mitigating undesired C-C bond-breaking steps that reduce the overall value/energy density of the biofuel. Such model-compound studies to inform the design of improved catalysts for HDO chemistry are necessary to improve the overall process economics/efficiencies for biofuels production. One important class of bio-derived compounds that has not been studied extensively with respect to HDO chemistry, particularly at the atomic level, is carboxylic acids. Past experimental work indicates that Pt/C and Pt/TiO2 catalysts are selective toward C-C and C-O bond-dissociation products for acetic acid HDO, respectively. To understand the role of Pt/TiO2 active sites in this observed change in selectivity and guide catalyst development, the work in this presentation focuses on modeling the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in acetic acid HDO. Density functional theory (DFT) calculations were performed using the Vienna Ab initio Simulation Package (VASP). The exchange-correlation functional was approximated by the Perdew-Burke-Ernzerhof functional. Dispersion interactions were captured using the D3 method. Projector augmented-wave potentials described electron-ion interactions, and electron wavefunctions were expanded via a planewave basis with an energy cutoff of 500 eV. Activation barriers were calculated using the climbing image nudged elastic band method. Results and Discussion: To discern the role of Pt-metal and Pt-TiO2 interface sites in promoting acetic acid HDO chemistry, Pt(111) slab and anatase TiO2(101)-supported Pt-nanowire (PtNW/OH-TiO2) surface models were constructed, respectively. Because H2 is co-fed in HDO reactions, the anatase support was terminated with OH groups. Interfacial vacancies have been shown to facilitate Ru/TiO2-catalyzed phenol HDO; thus, an interfacial model with an OH vacancy was also considered (PtNW/OHv-TiO2). Pt-TiO2-interface sites stabilize adsorption of all studied acetic acid HDO surface intermediates relative to terrace Pt-metal sites, particularly when an interfacial-OH vacancy is present. Oxygenated species prefer to bind at the OH vacancy through the O atom, suggesting a preference for C-O over C-C bond cleavage at these sites. This hypothesis is supported by net-negative and net-positive average shifts in the reaction energy and activation energy barriers for C-O and C-C bond-breaking steps, respectively, at Pt-TiO2-interface sites relative to Pt-metal sites. Using the calculated energetics, the predicted minimum-energy pathway was determined for each surface. Pt(111) is predicted to follow decarboxylation, producing undesired methane and carbon dioxide. Conversely, PtNW/OH-TiO2 and PtNW/OHv-TiO2 are both predicted to produce desired acetaldehyde and ethane. The interfacial vacancy may also play a key role in facilitating the first C-O bond-breaking step in acetic acid HDO, lowering the barrier by 0.6 eV relative to the defect-free interface model. These results demonstrate the critical role of the Pt-TiO2 interface in the shift in acetic acid HDO selectivity experimentally observed on Pt/C and Pt/TiO2 catalysts. The results herein demonstrate the important role of the Pt-TiO2 interface and interfacial oxygen vacancies in improving the carbon efficiency for HDO reactions in CFP upgrading.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

Catalytic Upgrading of Pyrolysis Products for the Production of Sustainable Aviation Fuel

The objective of this project is advance the state-of-technology for a catalytic fast pyrolysis (CFP) + hydrotreating (HT) process to produce sustainable aviation fuel and other biogenic products. Our approach focuses on performing integrated experiments using realistic biomass feedstocks and non-noble metal technical catalyst formulations. CFP is performed in an ex-situ configuration using a fluidized bed reactor without co-fed hydrogen. Research advancements over the past two years include establishing benchmark yield structures and compositional data for each step of the biomass-to-SAF process, demonstrating the ability to produce a cycloalkane-rich SAF product that meets key ASTM 4054 guidelines, generating benchmark characterization data for technical catalyst formulations with an emphasis on determining the unique composition and combustion properties of biogenic coke, and establishing bio-oil critical material attributes to mitigate the risk of plugging during down-stream hydroprocessing. Other impacts from this project include generation of broadly enabling scientific knowledge (12 publications/12 presentations since 2021), engagement with industry partners (Johnson Matthey, ExxonMobil, Phillips 66), and identification of a promising pathway to market that addresses emerging demands for biogenic refinery feedstocks.

biomass↗

Upconversion of non-recycled MSW paper fractions into biochar via slow pyrolysis and life cycle analysis: Pathways to net negative GHG emission

This study presents an integrated and sustainable approach to valorizing non-recycled municipal solid waste (MSW), a heterogeneous and underutilized waste stream destined for landfilling, by converting it into valuable biochar resources. Specifically, we investigated the upcycling of nonrecycled paper waste based on compositional analysis into four major fractions: high cellulose, high lignin, high contamination, and high ash content papers. These fractions were then homogenized and subjected to slow pyrolysis. The high cellulose fraction (36.1 %) was the most abundant, and contained 66.7 % cellulose, while the high lignin fraction showed the highest lignin (12.1 %) and carbon content (44 %), resulting in highest energy value of 17.4 MJ kg −1 . Biochar yields ranged from 25.6 % to 35.6 %, with the high ash fraction producing the highest yield and alkalinity (pH ≈ 11.2) due to its higher mineral content. Elemental analysis revealed enhanced carbon content up to 76.9 % and reduced oxygen and hydrogen, confirming effective carbonization. The high lignin-derived biochar showed the highest aromatic carbon content (82.8 %) and greater structural stability, while contaminated and ash-rich fractions exhibited dense, low-porosity surfaces due to the presence of contaminants and minerals. Spectroscopic analysis revealed degradation of carbohydrates, disappearance of cellulose peaks and formation of aromatic and mineral derived phases. The scaled life cycle process yielded a global warming potential (GWP) of 119.3 kg CO 2 -eq per ton of dry paper waste, offset by soil carbon sequestration of − 556.41 kg CO 2 -eq, resulting in a net impact of − 427.36 kg CO 2 -eq. This represents a net carbon removal exceeding by ~186 % the emissions associated with landfilling paper waste with electricity generation.

09 BIOMASS FUELS↗

Demonstration of low-level biogenic fuel content using quench curve and direct liquid scintillation counting (LSC) methods

In this work, an investigation into the direct method for liquid scintillation counting (LSC) quantification of biogenic fuel content in fuel blendstock is presented. This method development intentionally used a colored matrix (~99 wt%), fossil diesel fraction, and low-level biogenic fractions (~1 wt%) to determine the applicability of the LSC technique in colored blend mixtures. LSC procedures for quench correction, including the use of an instrument internal standard (Quantulus SQP values), color quench curves, and an internal 14 C standard spike on samples containing low-level amounts of biogenic gasoline, jet, and diesel mixed with fossil fuel, were compared. Samples were analyzed on both Perkin-Elmer Quantulus and Tri-Carb instruments, and the 14 C contents were compared with those determined by accelerator mass spectrometry (AMS). Results from the Tri-Carb instrument showed that percent differences of <10 % compared to AMS-reported values are achievable at 5-hour count times despite colored samples. A comparison between the impact of chemical and color quenching in the fuel samples showed that color quenching in highly colored samples reduces efficiency significantly more than chemical quenching, indicating that chemical quench curves are not appropriate for highly colored biofuel/fossil-fuel blended samples. Results indicate that both the direct method with internal spike quench correction and the use of a color-quench curve provide accurate results for 1 % biogenic fuel blends. Additionally, we have explored the use of Fourier transform infrared (FTIR) spectroscopy in measuring the biogenic content of the colored blended fuel samples. Preliminary results show the presence of biogenic carbon-derived fingerprints that are absent in fossil-derived sample. However, further work is needed to develop an FTIR-based quantitative method.

09 BIOMASS FUELS↗

Conserving asphalt resources: Rethinking rejuvenator performance evaluation through peptizing efficiency

Timely rejuvenation and restoration of asphalt are essential conservation practices that help preserve and extend the service life of roads, bridges, driveways, and parking lots. The performance of asphalt rejuvenators is often assessed based on their diffusion rates and softening power, yet these metrics alone fail to capture true rejuvenation potential. Here, this study integrates density functional theory (DFT) modeling with experimental analysis to show that rejuvenation effectiveness is primarily governed by molecular interactions with oxidized asphaltene nanoaggregates. DFT results revealed that amide- and unsaturated-chain compounds, such as hexadecanamide, oleic acid, and 9,17-octadecadienal, act cooperatively to disrupt π–π stacking and exfoliate asphaltene layers, reducing binding strength and enhancing dispersion. Unlike bulky, rigid molecules that remain trapped, these components remain mobile and repeatedly interact with multiple aggregation sites. Experimental validation using rheometry and FTIR confirmed that such molecularly compatible rejuvenators restore the binder flexibility and polydispersity, even when diffusion is relatively slow. Building on this mechanistic foundation, six rejuvenators (A2, A5, A7, A8, A9, and A10) were evaluated using a three-metric performance framework encompassing cracking resistance (Glover–Rowe parameter), UV stability, and surface hydrophobicity. Among the six rejuvenators evaluated, A9 exhibited the highest overall performance, reducing the Glover–Rowe cracking parameter by 85% (from 351 kPa to 53 kPa), demonstrating the greatest resistance to UV-induced aging with a stability index of 4.17 h·kPa⁻¹, and increasing surface hydrophobicity to a contact angle of 103.6°. Its superior performance is primarily attributed to its amide- and unsaturated-chain components, which act cooperatively to disrupt π–π stacking interactions and exfoliate asphaltene layers, thereby promoting molecular deagglomeration and enhancing long-term durability. These results shift the criteria for selecting rejuvenators: effective candidates must pair the electronic capability to unlock aged asphaltenes with sufficient structural stability to resist secondary aging and restore hydrophobicity. Restoring hydrophobicity is critical, as aging reduces the asphalt’s water repellency and increases water diffusion, which in turn accelerates moisture-related damage; consequently, a high-performing rejuvenator must effectively restore the binder’s hydrophobic characteristic. Collectively, these findings provide a framework for the rational design of next-generation of bio-based rejuvenators that enhance pavement longevity and promote long-term sustainability.

Aging↗

Predicting Catalytic Pyrolysis Aromatic Selectivity from Pyrolysis Vapor Composition Using Mass Spectra Coupled with Statistical Analysis

The behavior of fast pyrolysis (FP) and catalytic FP (CFP) of 20 renewable feedstocks was studied in a microscale reactor with molecular beam mass spectral analysis of products generated. A partial least-squares (PLS) model was constructed based on the FP vapor spectra that predicts the aromatic selectivity when upgrading over a ZSM-5 catalyst. Additionally, principal component analysis of both FP and CFP spectra was performed for comprehensive spectral analysis. This work highlighted the value of vapor-phase mass spectral screening to predict the subsequent feedstock performance and demonstrated that the quantity of coke deposited on the catalyst is not a reliable measure of catalyst deactivation when the feedstock type is varied.

09 BIOMASS FUELS↗

Desalting biocrude for improved downstream processing toward marine fuel application

Hydrothermal liquefaction of wet wastes (e.g., food waste and sewage sludge) offers a promising avenue for producing biocrude, but the resulting product is often contaminated with metals and water, impacting the biocrude upgrading steps to produce final fuel (e.g., jet and diesel). Here this study investigates the use of aqueous solutions of formic acid for desalting biocrudes and improving their quality. The results show that this approach significantly reduces both metal and water content, enabling mild hydrotreatment with reduced hydrogen consumption to further enhance the biocrude's quality. A preliminary technoeconomic analysis based on these experimental results shows that even without optimization, this washing process can yield biocrude with a minimum selling price of $1.87/GGE. Overall, our study demonstrates the potential for using dilute formic acid aqueous solutions to improve the quality of biocrudes, which can lead to more efficient and cost-effective conversion into biofuels.

09 BIOMASS FUELS↗

Decontamination of Mixed Paper and Plastic Municipal Solid Waste Increases Low and High Temperature Conversion Yields

With the implementation of China’s Green Fence Policy and the following National Sword Policy, there is a need to divert previously accepted waste materials away from the landfill. Mixed plastic and paper wastes that are too contaminated to be economically recycled can be used for conversion into fuels and products. The effect of common contaminants present in waste streams must be determined to make municipal solid waste (MSW) a viable alternative to agricultural feedstocks for conversion. In this study, MSW was sourced from a dual stream materials recovery facility (MRF) in Emmet County, Michigan and characterized via mass balance. The most common contaminants in mixed paper and plastic were quantified and targeted for decontamination when mixed paper was explored for low temperature conversion pathways and plastics for high temperature conversion pathways. Ink, stickies, and plastic contamination were sorted out of the mixed paper stream and did not have an impact on sugar yields during enzymatic hydrolysis (EH). Although no improvement in yield was found, it was noted that copy paper within the mixed paper stream had an elevated pH and higher concentration of fermentation inhibitors, suggesting that intrinsic properties of some paper types may not be ideal for EH and fermentation conversion. Dilute alkaline pretreatment and mechanical refining of mixed paper increased the EH yield of mixed paper, suggesting this previously established process could be used as a decontamination method. “Dirt” and particulates were washed from mixed plastic using either an aqueous detergent or a non-aqueous chemical washing method. Liquid oil yields were increased during microwave assisted fast pyrolysis. All decontamination techniques met the cost target of less than $30/dry ton with plastic decontamination ranging from $18.16 to $24.81/dry ton. Because dilute alkaline pre-treatment and mechanical refining is considered part of the conversion process, the decontamination cost during feedstock preprocessing was considered $0/dry ton.

09 BIOMASS FUELS↗

Techno-Economic Analysis for Co-Processing Fast Pyrolysis Liquid in Fossil Refineries

Recent work at the National Renewable Energy Laboratory (NREL) and throughout the bioenergy community has highlighted incentives associated with co-processing bio-intermediates in existing refineries to reduce capital costs associated with renewable fuels and chemicals production and reduce overall risk for emerging biomass conversion technologies. This presentation summarizes the techno-economic analysis results from the NREL-Petrobras collaboration that focused on refinery integration of fast pyrolysis oil through co-processing in the fluid catalytic cracking (FCC) process. The NREL-Petrobras work highlights the economic opportunity for refiners to engage in co-processing for low-carbon products and introduces the risks for refiners based on variability in crude and fossil-product markets. The NREL-Petrobras results also serve as a basis to inform policy design that reduces economic risk for refinery co-processing and repurposing opportunities. The final topics in the presentation highlight experimental capabilities and emerging analysis approaches at NREL and partner laboratories that support the development and commercial deployment of refinery utilization strategies.

bio-fuels↗

Drivers of Thermal Instability of Catalytic Pyrolysis Oils During Hydrotreating and Co-Processing to Sustainable Fuels

This presentation goes over polymerization observed in CFPs driven by thermally labile oxygenates. Lower oxygen oils have improved stability and a few percent decrease in oxygen greatly improves stability. Further improvements could be realized via targeted catalytic development and further reduction in reactive species. High stability CFP will help enable refinery integration of biogenic carbon.

bio-oil↗