Indirect evidence for elemental hydrogen in laser-compressed hydrocarbons
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70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
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Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbons with Renewable Feedstock
One of the grand challenges for national energy security is the establishment of sustainable chemical transformations. The chemical industry relies on naphtha feedstock from nonrenewable crude oil, and uses energy intense processes to make useful building block molecules such as ethylene through steam cracking, which generates significant greenhouse carbon dioxide emissions. Sustainable chemistry through selective catalysis should enable chemical transformations that use renewable feedstock such as nonfood biomass, minimize energy consumption, and do not emit greenhouse gases or other waste byproducts. In this research, we studied fundamental chemistry that couples the removal of oxygen atoms from nonfood biomass derived polyols and diols with oxidative dehydrogenation (ODH) of petroleum based alcohols. Heterobimetallic Re-Ir complexes were constructed and their reaction chemistry established. Typical substrates are glycerol, sugar alcohols and pentane to produce allyl alcohol, pentene, and water. The reaction mechanism of a recyclable rhenium nano-particle catalyst was established for deoxydehydration of sugar alcohols without the use of organic solvents.
09 BIOMASS FUELS↗
Catalytic oxidative coupling of arenes and alkanes: applications for efficient chemical synthesis and for hydrocarbon oligomerization. Progress Report 2016-7. Final report
This is the final report for DE-FG02-08ER15997 with a grant period of 8/15/2008-8/14/2018 (plus 1 year NCE); Program: Basic Energy Sciences; PI: Melanie S. Sanford; co-PI: Adam J. Matzger. The project resulted in 20 publications, 12 supported entirely by this grant and 8 supported substantially by this grant. The overall goals of this project were design catalysts (both homogeneous catalysts and MOF-supported catalysts) to control reactivity and selectivity in energy relevant C–H bond functionalization reactions. The proposed research led to a variety of new catalysts and catalytic processes which are currently finding application in organic synthesis. These efforts were well aligned with the goals of the DOE BES Catalysis Science Program. C–H functionalization reactions have extensive applications in energy-related industries, including petroleum and biofuels processing. The research activities also matched many of the priority areas identified by the Catalysis Science Program, including: investigating problems at the interface of heterogeneous and homogeneous catalysis as a means to derive new catalysts; incorporating 2° interactions to modulate catalyst stability, reactivity, and selectivity; using these new catalysts to tune molecular-level catalytic activity and selectivity; and studying structure-reactivity relationships of inorganic, organic, or hybrid catalytic materials in solution.
02 PETROLEUM↗
Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels (2019 State of Technology)
Each year, the DOE Bioenergy Technologies Office (BETO) assesses progress in their research and development efforts toward sustainable production of renewable fuels. Technical and cost targets were previously established for the wet waste hydrothermal liquefaction and biocrude upgrading pathway and summarized in a design report. The present report summarizes the research and associated techno-economic analysis (TEA) in support of the 2019 state of technology (SOT) assessment for this pathway. Data from Pacific Northwest National Laboratory’s Conversion hydrothermal liquefaction (HTL) program for wet waste was used to update the pathway techno-economic analysis (TEA) for the fiscal year 2019 State of Technology (2019 SOT). An overview of the current process model, experimental data and plant economics for the SOT is presented.
09 BIOMASS FUELS↗
Biochemical Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels and Products: 2019 State of Technology and Future Research
The purpose of this report is to benchmark the latest experimental developments across a number of potential bioconversion pathways as quantified by modeled minimum fuel selling prices (MFSPs), as a measure of current status relative to those final targets. For this state of technology, TEA models were run for two separate biological conversion pathways to fuels, based on available data for integrated biomass deconstruction and hydrolysate processing; namely carboxylic acids (primarily butyric acid) and diols (2,3-butanediol [BDO]), reflecting NREL’s recently-published 2018 biochemical design report focused on those two pathways. The models were run across three scenarios for lignin utilization, namely combustion, conversion to coproducts based on “base case” performance with biomass hydrolysate, and conversion to coproducts based on “high” performance demonstrated with model lignin monomer components.
09 BIOMASS FUELS↗
Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels: 2020 State of Technology
Data from Pacific Northwest National Laboratory’s conversion hydrothermal liquefaction (HTL) program for wet waste was used to update the pathway techno-economic analysis (TEA) for the fiscal year 2020 State of Technology (2020 SOT). The modeled fuel blendstock MFSP for the 2020 SOT is estimated at $4.50/GGE (with ammonia stripping of the AP), a reduction of $0.61/GGE, or 12%, relative to the 2019 SOT (Snowden-Swan et al. 2020). Progress in the HTL area includes increased reactor LHSV from 3.6 to 4.0 and a newly designed staged approach for the sludge pumping and heating, resulting in a 1 cent and 26 cent reduction in modeled MFSP, respectively. The newly designed heat exchanger configuration is less material and capital intensive than the previous SOT, and provides a system design that is more scalable with regard to practical fabrication limitations. Further improvements may be possible with the use of core inserts to enhance tube velocity and heat transfer rates. Biocrude hydrotreating research progress improved weight hourly space velocity (WHSV) from 0.67 to 0.72 hr-1 in the guard bed and from 0.39 to 1.02 hr-1 in the main hydrotreating bed, a 7% and 162% improvement, respectively. Hydrotreating performance was not sacrificed at the higher throughput rates and catalyst activity remained stable over the run. The demonstrated increase in WHSVs reduced the modeled MFSP by $0.34/GGE.
20 FOSSIL-FUELED POWER PLANTS↗
Hydrocarbon, Oxidation, Dehydrogenation and Coupling Over Model Metal Oxide Surfaces
Final report for a 24.5 year single investigator project aimed at understanding structure/function relationships in adsorption and reaction on metal oxide surfaces for understanding heterogeneous catalysis. An experimental surface science approach was taken using single crystal surfaces as model catalysts and supplemented by density functional theory (DFT) calculations. Materials studied experimentally and computationally include the base metal oxide SnO 2 and transition metal oxides α-Cr 2 O 3 , α-Fe 2 O 3 and MnO.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2021 State-of-Technology Cases
The Department of Energy’s (DOE) Bioenergy Technologies Office (BETO) aims to develop and deploy technologies to transform renewable biomass resources into commercially viable, high-performance biofuels, bioproducts, and biopower through public and private partnerships. BETO and its national laboratory teams conduct in-depth techno-economic assessments (TEA) of biomass feedstock supply and logistics and conversion technologies to produce biofuels. There are two general types of TEAs: A design case outlines a target case (future projection) for a particular biofuel pathway. It informs R&D priorities by identifying areas in need of improvement, tracks sustainability impact of R&D, and provides goals and benchmarks against which technology progress is assessed. A state of technology (SOT) analysis assesses progress within and across relevant technology areas based on actual results at current experimental scales relative to technical targets and cost goals from design cases, and includes technical, economic, and environmental criteria as available.
09 BIOMASS FUELS↗
Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2021 State-of-Technology Cases
The Department of Energy’s (DOE) Bioenergy Technologies Office (BETO) aims to develop and deploy technologies to transform renewable biomass resources into commercially viable, high-performance biofuels, bioproducts, and biopower through public and private partnerships. BETO and its national laboratory teams conduct in-depth techno-economic assessments (TEA) of biomass feedstock supply and logistics and conversion technologies to produce biofuels. There are two general types of TEAs: A design case outlines a target case (future projection) for a particular biofuel pathway. It informs R&D priorities by identifying areas in need of improvement, tracks sustainability impact of R&D, and provides goals and benchmarks against which technology progress is assessed. A state of technology (SOT) analysis assesses progress within and across relevant technology areas based on actual results at current experimental scales relative to technical targets and cost goals from design cases, and includes technical, economic, and environmental criteria as available.
09 BIOMASS FUELS↗
Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels: 2021 State of Technology
Each year the U.S. Department of Energy Bioenergy Technologies Office (BETO) assesses progress in their research and development efforts toward sustainable production of renewable fuels (DOE 2016) through the annual state of technology (SOT) assessment. The SOT assessment evaluates the impact of the year’s research progress on the modeled minimum fuel selling price (MFSP) for selected biofuel conversion pathways and measures the current state of the technology relative to defined goal case projections. Supply chain sustainability analysis to track and guide research toward improved greenhouse gas (GHG) emissions, energy usage, water usage and other environmental metrics for the pathway is performed by Argonne National Laboratory (Cai et al. 2018, 2020). Technical and cost targets for a projected goal case set for the year 2022 were previously established for the wet waste hydrothermal liquefaction (HTL) and biocrude upgrading pathway and summarized in a design report (Snowden-Swan et al. 2017). Process performance advancements made for HTL and biocrude hydrotreating have resulted yearly reductions in the modeled MFSP relative to the initial SOT (2018) (Snowden-Swan et al. 2020, 2021). This report summarizes the research and associated techno-economic analysis (TEA) for the pathway 2021 SOT. Methods and economic assumptions for the nth plant analysis used for the TEA are consistent with the design report (Snowden-Swan et al. 2017), with the exception of updates in the modeled cost year (2016) and income tax rate (21%).
09 BIOMASS FUELS↗
Direct conversion of Light Hydrocarbons to Olefins (Final report)
Reaction35 is developing a new industrial process that is substantially different from the traditional standalone dehydrogenation process practiced in industry such as Oleflex® and Catofin®. Those processes have substantial energy consumption and loss of feed constraints. The Reaction35 process is based on using molecular bromine to activate the alkane (e.g., nbutane) by forming highly reactive butyl bromides. The butyl bromides are easily converted to nbutylenes (final product) and hydrogen bromide. The hydrogen bromide generated in bromination and dehydrobromination is oxidized with air, recovering the molecular bromine which is reused. The overall result is a process with a favorably low energy consumption and less than 1 % overall loss of feed compared to more than 5 % for the direct dehydrogenation processes. During the grant period, several important aspects of the technology have been developed further. The major effort was the hydrogenation catalyst step development. The hydrogenation catalyst is used for recovery of the polybromobutanes to the bromobutanes intermediates. The scientific field regarding dibromo- and polybromoalkanes has not been extensively studied, which necessitated that Reaction35 performs a full study of a number of catalysts and the various experimental conditions that influence the hydrogenation reaction. Currently, Reaction35 has completed its catalyst selection and preliminary experimental parameters optimization. This will allow for the construction of an engineering model for a pilot unit testing.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels: 2022 State of Technology
Data from Pacific Northwest National Laboratory’s (PNNL) conversion hydrothermal liquefaction (HTL) program for wet waste was used to update the pathway techno-economic analysis (TEA) for the fiscal year 2022 State of Technology (2022 SOT). Figure S.1 shows the modeled minimum fuel selling price (MFSP) for the 2022 SOT, along with the previous years’ SOTs (Snowden-Swan et al. 2020, 2021, 2022). These costs are for a HTL plant scale of 110 dry ton/day sludge feed and a larger centralized upgrading plant scale of 38 million gallons/year biocrude feed, commensurate with the design case. All costs were updated to 2020 dollars. Corresponding cost breakdowns and technical parameters for each case are given in Appendix B. In previous years’ analyses options with and without ammonia (NH 3 ) stripping treatment of the HTL aqueous phase recycle stream were included in the analysis to account for cases with direct recycle of untreated HTL aqueous phase back to the wastewater treatment plant. In the FY21 SOT assessment however, system boundaries for the analysis were adjusted to reflect separate ownership/operatorship for the HTL plant and with that, nutrient surcharge fees associated with disposal of the aqueous phase wastewater to a municipal sewer system were incorporated to provide an improved accounting of true disposal costs for a standalone plant. With these changes, there is no significant cost difference between the case including ammonia removal and the case excluding ammonia removal and therefore the “no NH3 removal” options will not be included in the 2022 and future SOTs.
09 BIOMASS FUELS↗
Biochemical Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels and Products: 2022 State of Technology and Future Research
The annual State of Technology (SOT) assessment is a key activity for biochemical platform research. It allows the impact of research progress (both directly achieved in-house at the National Renewable Energy Laboratory [NREL] and indirectly extrapolated from available public data) to be quantified in terms of economic improvements in the overall cellulosic biofuel production process for a particular conversion pathway. As such, initial benchmarks can be established for currently demonstrated performance and progress can be tracked toward out-year goals to ultimately demonstrate cost-competitive biofuel technology. Building upon efforts to progress NREL's biochemical platform R&D work toward ultimate 2030 goals to demonstrate less than $2.50/gallon gasoline equivalent (GGE) fuel selling prices, experimental and techno-economic analysis (TEA) activities have primarily focused on "advanced" biochemical processing strategies to fuels and coproducts, guided by TEA modeling to highlight key barriers and priorities toward achieving this goal across a number of potential bioconversion pathways. The purpose of the present effort is to benchmark the latest experimental developments for these pathways as quantified by modeled minimum fuel selling prices (MFSPs), as a measure of current status relative to those final targets. For this SOT, TEA models were run for two separate biological conversion pathways to fuels, based on available data for integrated biomass deconstruction and hydrolysate processing; namely carboxylic acids (primarily butyric acid) and diols (2,3-butanediol [BDO]), reflecting NREL's recently published 2018 biochemical design report focused on those two pathways. The models were run across two scenarios for lignin utilization, namely combustion and conversion to value-added coproducts.
09 BIOMASS FUELS↗
Carbonate-Catalyzed CO 2 Insertion into Hydrocarbon C-H Bonds (Final Technical Report)
The development of methods to utilize CO 2 as a feedstock for chemical and fuel synthesis is critical for creating renewable alternatives to fossil fuel-based products. This project investigated a class of catalyst materials known as "dispersed carbonates", which are composed of alkali carbonate salts (e.g. potassium carbonate) dispersed in porous support materials. These catalysts react with CO 2 and organic molecules to form chemicals known as carboxylates that have wide applications in the chemical industry. The project used a combination of spectroscopic and reactivity studies to provide fundamental insight into the structure and mechanism of dispersed carbonates in these reactions, leading to variants with greater reactivity. In addition, dispersed carbonates were investigated for CO 2 hydrogenation catalysis, which is critical for processes under development for making sustainable fuels. The dispersed carbonates proved to be highly active and selective catalysts for the reverse water gas shift reaction in which CO 2 is hydrogenated to CO. The dispersed carbonates provide a compelling alternative to conventional metal-based catalysts for reverse water gas shift that could enable new process designs with higher efficiency and lower complexity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gas phase radical-radical chain reactions: Hydrocarbon growth without requiring reactivation.
Abstract not provided.
Couch, David↗
Ducted vs. Conventional Diesel Combustion with a Sustainable Hydrocarbon Diesel Fuel and Alkoxyalkanoate Blends at Idle and Moderate-Load Conditions.
Abstract not provided.
Nyrenstedt, Sven Anders Gustav↗
A Neural Network Based Model for Reactive Heavy Hydrocarbon Potential Energy Surfaces.
Abstract not provided.
Yang, Yoona↗