Engineering PapersSearch

SEARCH · Engineering Papers

Results for “Fischer-Tropsch”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

In-situ probing of the Fischer-Tropsch reaction on Co single crystal surfaces up to 1 bar

The surface chemistry of the Fischer-Tropsch catalytic reaction over Co has still several unknows. Here, we report an in-situ X-ray photoelectron spectroscopy study of Co$(0001)$ and Co$(10\bar{1}4)$, and in-situ high energy surface X-ray diffraction of Co$(0001)$ during the Fischer-Tropsch reaction at 0.15 bar - 1 bar and 406 K - 548 K in a H 2 /CO gas mixture. We find that these Co surfaces remain metallic under all conditions and that the coverage of chemisorbed species ranges from 0.4–1.7 monolayers depending on pressure and temperature. The adsorbates include CO on-top, C/-C x H y and various longer hydrocarbon molecules, indicating a rate-limiting direct CO dissociation pathway and that only hydrocarbon species participate in the chain growth. The accumulation of hydrocarbon species points to the termination step being rate-limiting also. Furthermore, we demonstrate that the intermediate surface species are highly dynamic, appearing and disappearing with time delays after rapid changes in the reactants’ composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

The role of manganese in CoMnO x catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis

Cobalt is an efficient catalyst for Fischer–Tropsch synthesis (FTS) of hydrocarbons from syngas (CO + H 2 ) with enhanced selectivity for long-chain hydrocarbons when promoted by Manganese. However, the molecular scale origin of the enhancement remains unclear. Here we present an experimental and theoretical study using model catalysts consisting of crystalline CoMnO x nanoparticles and thin films, where Co and Mn are mixed at the sub-nm scale. Employing TEM and in-situ X-ray spectroscopies (XRD, APXPS, and XAS), we determine the catalyst’s atomic structure, chemical state, reactive species, and their evolution under FTS conditions. We show the concentration of CH x , the key intermediates, increases rapidly on CoMnO x , while no increase occurs without Mn. DFT simulations reveal that basic O sites in CoMnO x bind hydrogen atoms resulting from H 2 dissociation on Co 0 sites, making them less available to react with CH x intermediates, thus hindering chain termination reactions, which promotes the formation of long-chain hydrocarbons.

36 MATERIALS SCIENCE

Author Correction: The role of manganese in CoMnO x catalysts for selective long-chain hydrocarbon production via Fischer-Tropsch synthesis

Correction to: Nature Communicationshttps://doi.org/10.1038/s41467-024-54578-3, published online 27 November 2024. The original version of this Article omitted a line in the Acknowledgements section: Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This has been now added into the last line of the acknowledgements section in both the PDF and HTML versions of the Article.

99 GENERAL AND MISCELLANEOUS

Research, Development and Demonstration of Advanced Vehicle Technologies in Clean Motor Fuels (CRADA Final Report)

NREL/DOE has been funding research, development, and demonstration (RD&D) projects to facilitate the deployment of alternative fuels into the marketplace in order to achieve three objectives: 1) enhance the reduction of mobile source emissions in California and the U.S.; 2) increase U.S. competitiveness and economic prosperity; and 3) preserve the environment through the reduction of emissions and toxins from the motor vehicle population. The Lewis-Presley Air Quality Management Act requires the South Coast Air Quality Management District to establish a program to encourage participation in projects to increase the utilization of clean-burning fuels. The parties seek to collaborate on a joint RD&D project to perform a field test on a small vehicle fleet operating on Fischer-Tropsch synthetic diesel fuel. Recently the 106th U.S. Congress designated "gas-to-liquid" (GTL) transportation fuels that are produced from domestic products as alternative fuels under the Energy Policy Act of 1992 (EPACT). Niche markets could develop quickly for these fuel products, perhaps especially for the use of Fischer-Tropsch synthetic fuels in centrally fueled vehicle fleets in California. NREL and its project partners from the U.S. Department of Energy and West Virginia University have recently conducted what we believe to be the first-ever controlled tests of Fischer-Tropsch synthetic fuels in heavy vehicles. These tests have shown that Fischer-Tropsch fuels can be substituted in unmodified trucks and buses without any detectable loss in drivability and performance. Compared to a California diesel fuel baseline, neat Shell Fischer-Tropsch fuel emitted about 12% lower NOx and 24% lower particulate matter over a five-mile driving route while maintaining the same fuel economy on an energy equivalent basis. Whereas these exhaust emissions reductions from these previous studies have been impressive, far greater exhaust emissions reductions can be achieved if the vehicles are retrofitted with emissions control technologies that are enabled by Fischer-Tropsch fuels. For this program, a test fleet would be selected and retrofitted with continuously regenerating traps (CRT’s) or diesel particulate filters (DPF's). The University of West Virginia, under a separate subcontract to SCAQMD will have the responsibility to test and measure the emissions from the test fleet of vehicles.

33 ADVANCED PROPULSION SYSTEMS

Intensified biogas to liquid (IBGTL) Process: Experimental validation and modeling analysis

The Intensified Biogas to Liquid (IBGTL) process aims to overcome traditional economy-of-scale barriers in biogas-to-liquid fuel production by integrating bi-reforming and Fischer-Tropsch synthesis (FTS) in a single IBGTL reactor. This reactor operates at uniform pressure with different optimized temperatures across two zones for efficient conversion, utilizing multifunctional bi-reforming catalysts and high-temperature FTS catalysts. Bench scale experiments were carried out using landfill gas (LFG) in a single pass process, and the yield data from these experiments were fed into process scale-up design and techno-economic analysis (TEA) across four scenarios: (1) a single pass process, (2) a process with material recycling, (3) a process with liquefied petroleum gas (LPG) co-product recovery, and (4) a process with electricity generation from the fuel gas produced. TEA identified Scenario 2 as the most cost-effective, achieving a Minimum Fuel Selling Price (MFSP) of $\$4.59$ per gallon, competitive with the current national diesel price of $\$4.7$ per gallon. However, comparison with the conventional two-reactor system highlights the need for catalyst performance improvements. Sensitivity analysis emphasized the importance of manufacturing cost, liquid fuel yield, and biogas flow rate. Further analysis determined that the IBGTL process must achieve a diesel mass yield beyond 11.7% to surpass the economic viability of the conventional TriFTS (Tri-reforming followed by Fischer-Tropsch Synthesis) process. If the IBGTL process attains the TriFTS yield of up to 17%, the resulting MFSP could be approximately 31% lower than the current TriFTS MFSP. Furthermore, renewable energy credits and carbon credits can further enhance the economic viability of BGTL processes.

09 BIOMASS FUELS

Preface: Special Issue: Catalysis for C1 Chemistry

This document is the preface for a Special Issue published in Catalysis Today that commemorates the career of Professor Jerry Spivey from LSU. It highlights the research contained in the special issue which represent areas in C1 catalytic chemistry where Professor Spivey made significant contributions. These areas include natural gas conversion, Fischer-Tropsch synthesis, superacid catalysis and more.

Fischer-Tropsch

SAF: a promising approach to meet growing jet fuel demand

SAF provides a promising approach to aid the rising jet fuel demand from increased travel around the world and reduce the lifecycle emissions from the aviation sector. Although the feasibility of SAF pathways has been demonstrated through economic and environmental metrics quantification, the models used to quantify these variables have a high degree of variability in terms of accuracy and thereby reliability. To understand how to adopt and commercialize SAF, we need to harmonize these process models and assess metrics and technical limitations related to their production technologies. We find the production cost of SAF using hydro processed fatty acids and esters (HEFA), Fischer-Tropsch (FT), and alcohol-to-jet (ATJ) to be $\$$3-$\$$6/gallon gasoline equivalent (gge) and life cycle emissions to be lower than Jet A, except for ATJ using corn grain (≤25%). HEFA utilizing oil feedstocks has the lowest production cost (~$\$$2.9/gge) and highest jet yield (>150 gge/dry ton), while FT has the largest emission reduction (94%) compared to fossil jet. A unique contribution of this study is a comparative analysis of metrics related to SAF processes across technical, economic, and sustainability aspects. A cross-comparison of these metrics shows HEFA using fats, oils, and grease have the most favorable ratings, while HEFA using algae and ATJ using corn stover have more neutral and unfavorable ratings, respectively. These ratings can be improved by implementing the right combination of practical and technological advancements.

09 BIOMASS FUELS

Sustainable aviation fuels from biomass and biowaste via bio- and chemo-catalytic conversion: Catalysis, process challenges, and opportunities

Sustainable aviation fuel (SAF) production from biomass and biowaste streams is an attractive option for decarbonizing the aviation sector, one of the most-difficult-to-electrify transportation sectors. Despite ongoing commercialization efforts using ASTM-certified pathways (e.g., lipid conversion, Fischer-Tropsch synthesis), production capacities are still inadequate due to limited feedstock supply and high production costs. New conversion technologies that utilize lignocellulosic feedstocks are needed to meet these challenges and satisfy the rapidly growing market. Combining bio- and chemo-catalytic approaches can leverage advantages from both methods, i.e., high product selectivity via biological conversion, and the capability to build C-C chains more efficiently via chemical catalysis. Herein, conversion routes, catalysis, and processes for such pathways are discussed, while key challenges and meaningful R&D opportunities are identified to guide future research activities in the space. Bio and chemo-catalytic conversion primarily utilize the carbohydrate fraction of lignocellulose, leaving lignin as a waste product. This makes lignin conversion to SAF critical in order to utilize whole biomass, thereby lowering overall production costs while maximizing carbon efficiencies. Thus, lignin valorization strategies are also reviewed herein with vital research areas identified, such as facile lignin depolymerization approaches, highly integrated conversion systems, novel process configurations, and catalysts for the selective cleavage of aryl C–O bonds. The potential efficiency improvements available via integrated conversion steps, such as combined biological and chemo-catalytic routes, along with the use of different parallel pathways, are identified as key to producing all components of a cost-effective, 100% SAF.

09 BIOMASS FUELS

Techno-economic analysis and network design for CO 2 conversion to jet fuels in the United States

The conversion of carbon dioxide (CO 2 ) into jet fuel holds significant potential for reducing CO 2 emissions, providing an alternative to carbon-based resources, and offering a renewable means of energy storage. The objective of this study is to conduct a techno-economic analysis and optimize the supply chain network for converting CO 2 to jet fuel in the United States, aiming to minimize total costs while assessing the environmental and economic feasibility of two CO 2 conversion pathways. This first pathway is based on Fischer-Tropsch synthesis (FTS), and the other one is based on the valorization and upgrading of light methanol (MeOH). Incorporating spatial and techno-economic data, a mixed-integer linear programming model was developed to select source plants and conversion pathways, locations of conversion refinery sites, and the amount of captured CO 2 across the United States. The optimal results indicate that the FTS pathway is adopted at all selected refineries when the hydrogen price is 1000 dollars/t and the operating cost, mainly electricity used in conversion, is reduced to 5 % of its current level. Under this scenario, the total annual profit is 8 billion dollars, and the net carbon emissions are -88,783,284 tons. The sensitivity analyses reveal that the prices of electricity and hydrogen significantly contribute to total production costs. The CO 2 recycle percentage of the FTS pathway influences the choice of applied pathways at refineries. Additionally, a higher conversion rate holds a substantial promise for reducing the total production cost and can make the MeOH pathway a viable choice.

10 SYNTHETIC FUELS

Development of a Techno-Economic Analysis Framework for a Solar Thermochemical Fuel Production Process

Synthetic liquid fuels can provide a drop-in substitute for fossil-based fuels in sectors such as aviation and maritime, where electrification is not a viable option due to the need for high specific energy density. However, for these alternative fuels to be adopted at a commercial scale, their price must be competitive compared to their fossil-based counterparts. The reverse water-gas shift (RWGS) reaction offers a promising pathway, using hydrogen (sourced from electrolysis) and carbon dioxide as the feed and reacting to produce syngas - a mixture of H2 and CO at a specific ratio. Syngas is a useful precursor that can be converted into fuels and chemicals via known downstream processes, such as liquid transportation fuels via Fischer-Tropsch (FT) synthesis. The RWGS reaction is currently not applied in commercial scale, unlike the rest of the components in the process chain (electrolyzers and syngas-to-fuel synthesis units). The RWGS reaction poses several challenges due to its restrictive thermodynamics. Being an equimolar reaction, high temperatures and a large excess of H2 are needed to achieve reasonable CO2 conversion at equilibrium. This has detrimental effects on practical process implementation and the quality of syngas that can be produced, with direct effect on the energy and capital requirements, as well as the need for expensive downstream separation. In this work, we are proposing to develop a new concentrating solar thermal (CST) compatible RWGS reactor, performing the reaction in a 2-step chemical looping process using metal oxide at a temperature range of 600-800 degrees Celsius. By decoupling the reactor from the solar receiver, the Generation 3 (Gen3) CST technology could be utilized, together with its proposed thermal energy storage (TES) technology, benefitting from a good match to the required temperatures. CST technology is a viable option for supplying the heat that could be rapidly deployed in scale, thus being a good match to the gas-to-liquid (GTL) process which requires a large minimal scale to be commercially viable. The integration of TES with CST also allows operating the plant at large annual capacity factors and avoids multiple shutdown/startup cycles, thus fitting into the steady-state operation mode that most GTL processes require. The main innovation in the proposed design hinges on a countercurrent reaction design using a packed bed reactor. In 2019 Metcalfe et al. showed the benefits of countercurrent species exchange could be realized in a redox chemical-looping processes, by storing the favorable countercurrent chemical potential profiles in a packed bed of non-stoichiometric oxide. Metcalfe et al. applied this breakthrough concept to the WGS reaction, which is conventionally a co-feed catalytic process, showing a dramatic improvement. Bulfin et al. (2023) performed a similar proof-of-concept demonstration for the RWGS reaction using CeO2, achieving cumulative and peak CO2 conversions of 88% and 95%, respectively, compared to a thermodynamic limit of 58% for the co-feed catalytic process at the same conditions. In our new REGENLOOP project, we are developing a reactor prototype from the heat-exchange packed bed reactor-type, a commonly used reactor in the chemical industry. The endothermic heat of reduction will be supplied to the reactor using CST, while the same heat transfer fluid (HTF) mechanism will be used to extract the exothermic heat of oxidation. An array of multiple reactors is used to supply constant high-purity CO stream, that is then mixed with H2 from electrolysis to produce a high-purity syngas at the required composition. By removing the CO-CO2 separation after the RWGS process, significant energy and cost reduction can be achieved. A physics-based TEA framework is currently being developed, covering all the major plant processes, from the solar collection through storage, chemical looping RWGS, GTL, and auxiliary unit operations, up to the liquid hydrocarbon product. This modeling framework will utilize reduced-order models for the chemical looping RWGS and TES, CST modeling using SolarPILOT, and Aspen Plus for the GTL. By using this combined physics-based approach, the effects of design/operating parameters on the performance and cost can be elucidated. In our presentation, the modeling framework will be presented in detail, including preliminary cost predictions of using this plant configuration under a few selected relevant case studies. This study will be used to identify the major cost drivers, informing further system design and optimization needed to chart the way for a commercially viable pathway.

14 SOLAR ENERGY

Integrating Phase Change Materials within Catalysts for Effective Heat Management

Here, most fuel conversion technologies, including Fischer-Tropsch synthesis, C-C coupling, methanol synthesis, and aldol condensation reactions, are highly exothermic, making precise temperature control essential to avoid thermodynamic limitations while maintaining selectivity and catalyst stability. Current industrial practice mitigates these effects primarily through reactor-level, ex situ temperature control strategies — such as heat exchangers, multi-tubular reactors, or quench cooling — but these approaches fall short in regulating the heat generated, transported, and dissipated at the catalyst particle scale.

Karakaya, Canan [Oak Ridge National Laboratory (OR

The role of transition metal formyl intermediates in the reduction of CO and CO 2

Transition-metal formyl (metalloformyl) complexes occupy a central position in the activation of small molecules, particularly in the reduction of carbon monoxide (CO) and carbon dioxide (CO 2 ). This review examines five decades of progress in the synthesis of metalloformyl complexes and investigations into their structure and reactivity. The bonding in the M–CHO unit is best described as a resonance hybrid between a classical σ-bound formyl ligand and an oxycarbene-like electronic structure, which governs their distinctive spectroscopic signatures and versatile reactivity. Established synthetic routes are summarized, including pathways involving hydride addition and CO insertion, alongside a discussion of the thermodynamic and kinetic factors that control formyl stability. Decomposition pathways and Lewis-acid stabilization strategies are analyzed as key design principles for extending metalloformyl lifetimes under catalytic conditions. Particular attention is given to hydride transfer processes and the role of metalloformyl intermediates as both reactive substrates and hydride sources in reduction chemistry. Lastly, emerging catalytic strategies that exploit metalloformyl intermediates in CO 2 and CO reduction are evaluated, highlighting how control of hydricity, redox potential, and secondary-sphere interactions enables selective C—H bond formation under comparatively mild conditions. Collectively, these studies establish metalloformyl complexes as mechanistically informative and functionally relevant intermediates that bridge fundamental organometallic chemistry with modern approaches to small-molecule activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Hydrogen Adsorption, Reactivity, and Catalysis on Colloidal Iron Carbide Nanoparticles

Supported iron carbide particles have long served as catalysts for CO hydrogenation (the Fischer Tropsch synthesis, FTS) and continue to be attractive. Despite this, little is known about their chemistry. Reported here is a colloidal Fe x C nanoparticle (NP) model system that allows direct observation of surface hydrogen and CO, as well as quantification of the surface H. Dodecylamine-capped Fe x C NPs (DDA-Fe x C NPs) were synthesized through solution-phase carburization of Fe NPs and form stable colloids in low-polarity organic solvents. Treatment of these colloids with H 2 or D 2 produced highly hydrogenated materials, and FTIR spectra of DDA-Fe x C-D n showed that most of the D binds to carbides, with at least four distinct v(C-D) modes. The surface C-H(D) bonds were all reactive, transferring hydrogen to alkenes and other reagents in solution. Titration and ICP measurements showed a 0.17:1 ratio of added H:total Fe, or roughly. 40 H per 1.8 nm DDA-Fe x C NP. Conversely, CO was preferentially bound to surface Fe sites, with FTIR spectra showing a single broad v(CO) that shifted with CO coverage or co-adsorption of H 2 . The DDA-Fe x C NPs were active catalysts for both olefin hydrogenation and the FTS, under mild conditions and without catalyst pre-treatment. The CO hydrogenation reactions yielded a broad distribution of long-chain linear paraffins and olefins. Though quantitative comparisons with typical FTS results are not possible because of our use of sealed batch reactors and other factors, the observations of high catalytic reactivity demonstrate the relevance of this model system to iron-carbide catalysis. DFT calculations on model slab surfaces with varying iron carbide stoichiometries revealed that the thermodynamically preferred surface adsorption sites are C for H ads and Fe for CO ads . A variety of binding sites and binding energies were found for each adsorbate. We are unaware of previous studies indicating that a diverse array of C-H bonds is the primary source of reactive H on iron carbides. Experimentally, the diversity of *C-H sites was evident in reactions with H-atom donors and abstractors of different strengths, from both the reaction stoichiometries and IR spectra. The different surface–H binding energies correlate with the v(C-D) stretching frequencies. Furthermore, these insights into complex iron carbide surfaces and catalysis could assist catalyst design, and they showcase the importance of stoichiometric studies of reaction intermediates.

08 HYDROGEN