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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.
Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels
NREL's thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient route to completely biogenic pyrolysis-based fuel precursors, fuels, and value-added chemicals depending on catalyst and process conditions. A near term pathway being developed uses these liquids for co-processing with petroleum feedstocks to assess biogenic carbon incorporation in hydrocarbon fuel feedstocks for potential refinery use. In this work, the impact of feedstock and catalyst on catalytic fast pyrolysis oil (CFPO) composition was determined with the oils then assessed for biogenic fuel production via FCC (fluidized catalytic cracking) co-processing. Biomass vapors were generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce clean vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled to a custom pyrolyzer system designed to produce consistent-composition pyrolysis vapors as feed to the DCR. Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available modified zeolite-based catalysts to produce CFPOs. These upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and simulated distillation (SIMDIS) to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. These exploratory vapor-phase-upgrading results demonstrated the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The FCC co-processing results demonstrated the feasibility of using CFPOs with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.
Industrial Requirements Status Report and Down-Select of Candidate Technologies
The report discusses the potential for implementing Integrated Energy Systems (IES) using advanced nuclear reactors to provide thermal and electrical energy to carbon-emitting industries while reducing their carbon footprint. Nine different industries were reviewed to determine their decarbonization potential, how nuclear power can fit in, and the carbon footprint of each. The report also identifies specific integration points and streams for most processes, including temperature and pressure requirements of integrating nuclear power with industrial processes. The report also provides insights on advanced nuclear reactors and their potential for us in IES for decarbonization. The target audience for the report is broad, but mainly addressed to the industry leads and nuclear reactor developers. The report recommends that in the short term, a few processes should be identified to continue research and investigation so that front end engineering design work can provide technical analysis for integrating nuclear heat and replacing existing carbon-emitting thermal sources. The work emphasized the significant decarbonization opportunity across each of the technologies looked at as well as how novel and useful nuclear integration is to reduce the environmental impact of these significant industries.
Life-cycle energy use and greenhouse gas emissions of palm fatty acid distillate derived renewable diesel
This study aims to quantify life-cycle fossil energy use and greenhouse gas (GHG) emissions for palm fatty acid distillate (PFAD) derived renewable diesel (RD) taking into consideration different feedstock classifications that are applicable to PFAD (residue, byproduct, or coproduct), and incorporating updated data for key processes. Under the three classifications, the PFAD to RD pathway was modeled using the Greenhouse gases, Regulated Emissions, and Energy Use in Technologies (GREET®) model. PFAD-derived RD could reduce fossil energy consumption by 77%–88%, relative to petroleum diesel. GHG emissions are very sensitive to PFAD classification and coproduct handling methods. Considering the production of palm oil and PFAD and economic value, we maintain that PFAD should be treated as a byproduct in palm oil refineries. With this treatment, PFAD-derived RD could achieve 84% GHG emissions reductions, compared to the emissions of petroleum diesel. We also employed a substitution method to address the substitution of PFAD by other materials in the marketplace. Compared to coproduct allocation results, we found substituting PFAD by tallow, soy oil, barley, and canola oil results in lower GHG emissions. Due to high induced land-use change emissions associated with palm farming, if PFAD is treated as a coproduct with refined palm oil, PFAD-derived RD may not deliver GHG reductions. A sensitivity analysis identified key parameters such as palm fruit yield, oil extraction efficiency in oil mills, and energy use intensity for RD production affects LCA results significantly; future efforts to improve these parameters could result in further GHG reductions.
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
Opportunities and Challenges for Hydrotreating of Catalytic Fast Pyrolysis Oil to Fuels
Catalytic fast pyrolysis (CFP) provides a versatile platform for producing fuels to combat climate change and meet decarbonizing targets. In this contribution, we will discuss the hydroprocessing of CFP oils to a variety of fuels, including sustainable aviation fuel (SAF), diesel, and marine fuel. Both standalone and co-hydroprocessing with petroleum streams will be covered. Hydrotreating CFP oil at temperatures around 400 Degrees Celsius can produce a highly deoxygenated product with oxygen contents below the detection limit. However, the quality of fuel fractions produced has been a problem, manifesting as low octane numbers for the gasoline-range fraction and low cetane numbers for the diesel-range fraction. Incorporating an initial transition zone for hydrogenation during hydrotreating was shown to dramatically increase the diesel fraction cetane number from 24 to 45. A similar approach enabled the production of a cycloalkane-rich SAF fraction meeting key ASTM 4054 guidelines with respect to density, viscosity, heating value, volatility, freeze and flash point. Over 400 hours of hydrotreating for SAF was demonstrated with no signs of catalyst bed fouling, measured by pressure drop over the catalyst bed. Compared to other fuels, marine fuel is unique in that it does not require complete deoxygenation. We investigated the minimum hydrotreating requirements to produce fuel compatible with very low sulfur fuel oil, and the results suggested 30% reduction in hydrotreating costs for this approach. Co-hydroprocessing offers an opportunity to take advantage of refinery infrastructure and economies of scale although the operation is less flexible with respect to operating conditions. Co-hydroprocessing CFP oil with petroleum streams gave efficient deoxygenation at milder conditions (e.g. at temperatures of 320 Degrees Celsius) than required for standalone hydrotreating. Over 90% incorporation of biogenic carbon in the CFP oil was confirmed by carbon-14 analysis. Hydrotreating of CFP oil, whether by standalone or co-processing, can produce a variety of fuel cuts, whose quality can be tailored by changing process conditions. Challenges remain, including long-term catalyst performance and determining CFP oil quality requirements.
Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels
NREL’s thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient and economical route to completely biogenic pyrolysis-based fuel precursors, potential fuels, and value-added chemicals depending on catalyst choice and process conditions. In this approach, biomass vapors are generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce conditioned vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled with a custom pyrolyzer system designed to produce consistent composition pyrolysis vapors as feed to the DCR. The coupled system is shown below (Figure 1). Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available and laboratory modified zeolite-based catalysts. Upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and micro distillation to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. Measured process parameters identified from technoeconomic process analysis included achieving oil oxygenate contents of 20% or less, carbon-conversion efficiencies of 30% or more, and catalyst coking rates of 10% or less. A proprietary modified zeolite catalyst from Johnson Matthey produced oils that met these requirements. Using the DCR equipped with a proprietary nozzle system, a second approach focused on reducing the carbon intensity of petroleum-derived hydrocarbon fuels by FCC co-processing these CFP oils with petroleum vacuum gas oil (VGO) to produce biogenic carbon containing fuels. The vapor-phase upgrading results demonstrated for the first time the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The co-processing results demonstrated the feasibility of using CFP oils with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.
Comparative Techno-economic Analysis and Life Cycle Assessment of Producing High-Value Chemicals and Fuels from Waste Plastic via Conventional Pyrolysis and Thermal Oxo-degradation
The rapid rise in global plastic production in recent decades has resulted in the massive generation of plastic waste. Over 75% of the plastic waste generated in the United States was sent to landfills, with a meager 8.7% recycled. Plastics are valuable feedstocks for platform chemicals and fuels. Chemical upcycling of waste high-density polyethylene (HDPE) is gaining more attention as a potentially feasible and environmentally friendly plastic waste management technology. Conventional pyrolysis (CPY) and thermal oxo-degradation (TOD) are two chemical upcycling technologies actively researched for decomposing waste HDPE into valuable chemicals and fuels. However, there are few studies on the techno-economic analysis (TEA) and life cycle assessment (LCA) of these technologies for converting waste HDPE to valuable products. This study conducts a comparative TEA and LCA study of the thermochemical decomposition of waste HDPE to produce gaseous (ethylene and propylene) and liquid (naphtha, diesel, and wax) products by CPY and TOD. The study elucidates and compares the impact of hydrocracking longer chain hydrocarbons to produce more valuable products on the TEA and LCA. The TEA showed that the fixed capital investment could range from $\$32.5$ million for TOD without hydrocracking to $\$244$ million for CPY with hydrocracking scenarios. Annual revenues range from $\$28.1$ million to $\$71.5$ million in favor of scenarios with hydrocracking. However, the net present value ranges from $\$1.4$ million to $\$265.8$ million in favor of scenarios without hydrocracking. Sensitivity analysis showed that fixed capital cost, facility capacity, and product prices have the biggest impact on the process economics of the facilities, while utilities and waste transportation to refineries have the biggest impact on environmental impacts. Here, the LCA showed that primary products from scenarios without hydrocracking can be more environmentally friendly than virgin products from petroleum processes. However, TOD and CPY with hydrocracking primary products have more emissions than those of virgin products.
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.
Sustainable Aviation Fuel Blending and Logistics
Worldwide, aviation accounts for 2% of all manmade carbon dioxide emissions and 12% of all transportation CO2 emissions. In 2023, the U.S. accounted for 27% of the world jet fuel consumption. The aviation industry has set sustainability goals, and mandates. Sustainable aviation fuel (SAF), made from nonpetroleum feedstocks, significantly reduces aviation emissions. SAF must be blended with petroleum-based jet fuel prior to its use in aircraft. Jet fuel quality standards and certification documents are essential to fuel performance, operability, and safety and are the primary driver in determining locations for blending. Several locations were evaluated including terminals, airports, refineries, and greenfield/brownfield sites. While all the locations evaluated are technically capable of blending fuel, there are practical considerations that make terminals the optimal location for blending. The report includes background on jet fuel and SAF use, fuel quality standards, modes of transport for both conventional jet fuel and SAF, and terminal information.
The Novel Charfuel® Coal Refining Process 18 TPD Pilot Plant Project for Co- Producing an Upgraded Coal Product, and Commercially Valuable Co- Products: Area of Interest #3 – Coal Beneficiation Pilot Plant Testing (Final Report)
Operation of Carbon Fuels, LLC’s (“CF”) existing, permitted 18 TPD pilot plant located in Golden, Colorado using two individually ranked (ASTM D 388) coal types (two campaigns), employing the novel Charfuel® coal refining process to produce an upgraded coal product and a number of high-valued organic and inorganic coproducts (for which there presently exists large commercial markets) in order to produce engineering and product data which will then be utilized toward the design of a commercial scale integrated facility (pre-feed document). Carbon Fuels, LLC has developed the Charfuel® Coal Refining Process which refines domestically abundant, raw coal (in the same manner as crude oil is refined) to produce the identical, high value co-products that are refined from crude oil. Thus, gasoline, jet fuel, “green diesel”, fuel oil, and marine fuels, as well as petrochemicals such as benzene, toluene, xylene, and methanol are refined from raw coal using this process. The Charfuel® Coal Refining Process is not a coal conversion process, like pyrolysis, or indirect liquefaction. Nor is it an alternative energy system. Rather it is a coal refining process that has the ability to economically produce products traditionally associated with the refining of crude oil but using only abundant, raw coal as the refinery feed stock. The Charfuel® Coal Refining Process is more economical than crude oil refining and is environmentally benign. Therefore, this value added process yields a return on investment well above 50% for a commercial facility. Furthermore, the Charfuel® process, unlike alternatives such as ethanol and hydrogen, can utilize the existing transportation, delivery, and other petroleum based systems. Hence, there is no need for new engines, pipelines, tankers, or product acceptance. As a result, the profitability of the process is increased. Objectives: (1) Operation of the integrated 18 tpd pilot plant, using two coal types (ranks); (2) Demonstration of process flexibility in being able to produce different products (gas, liquid, and char), as well as determination of operating parameters for identifying scale up criteria for two coal types (ranks); (3) Generation of engineering and design information (process specifications) for use in designing a commercial scale plant (scale-up); (4) Determination of important environmental issues surrounding the process and the products such as fate of trace elements (mercury and other heavy metals) and distributions of SO2, NOx, and CO 2 by analysis of effluent streams; (5) Production of sufficient product to allow reliable commercial economic evaluation of both the refined coal product and the coproducts; and, (6) Assessment of longer-term reliability of unit operations. Period 1: reconfiguration of the 18 TPD plant to meet specific FOA requirements and to qualify the facility for operation; and, Period 2: operation of the 18 TPD plant for two campaigns using two coals types (ranks) which are widely commercially used and abundant - the first being a subbituminous (Powder River Basin (“PRB”)) coal, and the second a bituminous (Illinois #6) coal.
Recent progress in the synthesis of advanced biofuel and bioproducts
Energy is one of the most complex fields of study and an issue that influences nearly every aspect of modern life. Over the past century, combustion of fossil fuels, particularly in the transportation sector, has been the dominant form of energy release. Refining of petroleum and natural gas into liquid transportation fuels is also the centerpiece of the modern chemical industry used to produce materials, solvents, and other consumer goods. In the face of global climate change, the world is searching for alternative, sustainable means of producing energy carriers and chemical building blocks. The use of biofuels in engines predates modern refinery optimization and today represents a small but significant fraction of liquid transportation fuels burnt each year. Similarly, white biotechnology has been used to produce many natural products through fermentation. The evolution of recombinant DNA technology into modern synthetic biology has expanded the scope of biofuels and bioproducts that can be made by biocatalysts. Furthermore, this opinion examines the current trends in this research space, highlighting the substantial growth in computational tools and the growing influence of renewable electricity in the design of metabolic engineering strategies. In short, advanced biofuel and bioproduct synthesis remains a vibrant and critically important field of study whose focus is shifting away from the conversion of lignocellulosic biomass toward a broader consideration of how to reduce carbon dioxide to fuels and chemical products.
Milligrams to kilograms: making microbes work at scale
Energy is one of the most complex fields of study and an issue that influences nearly every aspect of modern life. Over the past century, combustion of fossil fuels, particularly in the transportation sector, has been the dominant form of energy release. Refining of petroleum and natural gas into liquid transportation fuels is also the centerpiece of the modern chemical industry used to produce materials, solvents, and other consumer goods. In the face of global climate change, the world is searching for alternative, sustainable means of producing energy carriers and chemical building blocks. The use of biofuels in engines predates modern refinery optimization and today represents a small but significant fraction of liquid transportation fuels burnt each year. Similarly, white biotechnology has been used to produce many natural products through fermentation. The evolution of recombinant DNA technology into modern synthetic biology has expanded the scope of biofuels and bioproducts that can be made by biocatalysts. This opinion examines the current trends in this research space, highlighting the substantial growth in computational tools and the growing influence of renewable electricity in the design of metabolic engineering strategies. In short, advanced biofuel and bioproduct synthesis remains a vibrant and critically important field of study whose focus is shifting away from the conversion of lignocellulosic biomass towards a broader consideration of how to reduce carbon dioxide to fuels and chemical products.
Front-End Engineering Design for Carbon Capture from Shell's Deer Park Chemical Complex (Final Scientific/Technical Report)
This is the final scientific/technical report for a Front-End Engineering and Design (FEED) whose objective was to separate and capture over 820,000 tonnes per year (tpy) CO2 emissions from the commercially operated Shell Chemicals Complex located in Deer Park, Texas, USA reducing the overall facility CO2 emissions by 95% while providing energy transition jobs in a commercial area with a high concentration of refinery and chemical facilities producing CO2 emissions. The emission sources at the facility that were in scope were a total of Sixteen Furnaces – 8 OP3 furnaces and 8 OP3/HT2 Furnaces. Other minor sources were out of scope.
Diesel-like Fuels, Combustion, and Emissions
The need to reduce the carbon footprint from medium- and heavy-duty diesel engines is clear; low-carbon biofuels are a powerful means to achieve this. Liquid fuels are rapidly deployed because existing infrastructure can be utilized for their production, transport, and distribution. Their impact is unique as they can decrease the greenhouse gas (GHG) emissions of existing vehicles and in applications resistant to electrification. However, introducing new diesel-like bio-blends into the market is very challenging. At a minimum, it requires a comprehensive understanding of the life-cycle GHG emissions of the fuels, the implications for refinery optimization and economics, the fuel’s impact on the infrastructure, the effect on the combustion performance of current and future vehicle fleets, and finally the implications for exhaust aftertreatment systems and compliance with emissions regulations. Such understanding is sought within the Co-Optima project.
Towards Net-Zero: Nuclear-Assisted Waste Biomass to Liquid Fuel in Eastern Idaho
A nuclear assisted carbon negative hybrid energy process that enables production of synthetic bio-crude oil and biochar from Eastern Idaho waste biomass is proposed. The process integrates nuclear powered electricity with high temperature steam electrolysis and biomass hydropyrolysis. The bio-crude oil is of sufficient composition and blended with traditional crude oil at a refinery. Hydrogen from the electrolyzer is pressurized and inserted into the pyrolyzer. Non condensable gases generated in the hydropyrolysis process are burned with oxygen from the electrolyzer to produce heat for the electrolyzer, biomass dryer, and pyrolyzer. The biochar is returned to the soil via fertilizer application and remains there for thousands of years. Since the total process uses nuclear generated electricity, the carbon in the biochar is ultimately sequestered from the atmosphere, thus making the process carbon negative. Using Eastern Idaho wheat or barley straw, this hybrid energy process has the potential to provide an alternative petroleum source. Two options exist for the system design: 1) send electricity from the nuclear plant and straw to a chemical processing plant to produce the bio-crude and biochar, 2) construct the biomass processing facility near the nuclear plant to allow use of nuclear-generated process heat to drive the chemical. Process model description and results are discussed. The process is sized to produce gasoline and diesel at the rate that the INL uses every day for fleet usage.
Using Separation-Enhanced Isotope Ratio Mass Spectrometry to Enable Increased Renewable Carbon Content in Transportation Fuels (CRADA 525)
Stable isotope ratio measurements of carbon atoms using isotope ratio mass spectrometry (IRMS) can be an effective tool for quantifying biogenic carbon in co-processed fuels, with results approaching the precision and accuracy of accelerator mass spectrometry (AMS). The lower cost of an IRMS may enable deployment to refineries, improving access and analysis turnaround times (≤2 hours), and, by extension, provide data that can allow process optimization to maximize renewable carbon in desired refinery products. This project explored the integration of chemical separation with IRMS analyses to enable highly detailed tracking of biogenic carbon into fuel product streams separated by boiling point range, chemical class, or specific compound. Forty-nine fuels and fuel components of fossil and biogenic origin, spanning gasoline and diesel boiling point ranges, were received from three refiners and were analyzed for their δ 13 C values via IRMS. Results spanned a 13 C range from ca. 10‰ to 44‰ and reflect materials derived from sustainable sources (e.g., C4 or C3 plants, animal-based pathways, syngas) or from fossil-derived fuels. Common ranges are approximately 18‰ to 9‰ and approximately 30‰ to 20‰ for C4 and C3 plants, respectively, and approximately 34‰ to 24‰ and approximately 70‰ to 33‰ for petroleum-derived fuels and methane, respectively. Fuel-like standards were developed and tested using direct-injection elemental analyzer (EA) IRMS for liquid fuels. This method was compared with the published methods, yielding statistically similar results. Four blend curve sets were produced ranging from 0% to 100% of a fuel containing biogenic carbon, focusing on 0% to 10% biogenic carbon. Linear fits were the most applicable for two of the four blend curve sets; however, two sets were found to exhibit slightly quadratic behavior, which was more pronounced in low biogenic blend samples, necessitating second-order fits. The origin of the slight quadratic behavior remains unclear; however, the discussion points to possible interpretations. CanmetENERGY thoroughly characterized a majority of the samples using one- and two-dimensional gas chromatography (GC and GC×GC, respectively) and other analyses. Selected samples were subjected to solid phase extraction (SPE) for saturate, olefin, aromatic, and polar (SOAP) analysis, and the resulting solvent-diluted fractions containing saturates and aromatics were returned to Pacific Northwest National Laboratory (PNNL), where the solvent was removed via evaporation or physical separation using GC techniques. Characterization and separations provided an understanding of saturate and aromatic content, as well as boiling point ranges for each sample and sample fraction. Samples resulting from SPE were examined using EA-IRMS and gas chromatography combustion IRMS (GC-C-IRMS) analyses. Both approaches suggest that the range in values between end-members can be increased by selecting the paraffinic or aromatic fraction of the end-member or by selecting among individual compounds resulting from GC separation of the paraffinic fractions. Considerable work remains to put these approaches into practice and statistically validate the benefit for using a fraction or individual compound over bulk analysis of a sample. However, initial results suggest that separations provide advantages for samples having blend ratios of less than 10% biogenic blendstocks. 13 C results showed statistically similar biofuel blend results to those obtained at PNNL, although additional work is needed to obtain better reproducibility. Select samples were sent to Los Alamos National Laboratory (LANL) for IRMS measurements and Beta Analytics for AMS measurements. This work suggests that IRMS and AMS yield closely comparable results and in some circumstances, IRMS could serve as a surrogate for AMS. While additional work is needed to better resolve statistical advantages for separations and better show the comparable nature of IRMS and AMS in both the biogenic carbon analysis of bulk chemical classes, initial results from this study suggest that these should be pursued in order to proliferate this approach for quantifying biogenic carbon in transportation fuels to the refinery level, thereby potentially enabling process optimization in co-processing scenarios.