Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Olefins”

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.

At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Direct Conversion of CO 2 to Olefins over a Cr 2 O 3 /ZSM-5@CaO Cooperative and Bifunctional Material Under Isothermal Conditions

Direct conversion of point-source CO 2 into fine chemicals over cooperative and bifunctional materials (BFMs) – composed of adsorbents and catalysts – has emerged as a promising approach to improve the energy efficiency of the carbon capture and conversion processes. In this study, a bifunctional material consisting of Cr 2 O 3 /ZSM-5 catalyst and CaO adsorbent was developed and tested in the CO 2 -oxidative dehydrogenation of propane (CO 2 –ODHP) for reactive capture of CO 2 in a fixed bed reactor. First, CaO was prepared using two distinct methods: solid-state and citrate sol–gel. The citrate sol–gel method resulted in small and finely-distributed CaO particles, allowing more accessible sites for CO 2 adsorption. Consequently, a high CO 2 adsorption capacity of ~14 mmol/g was achieved with fast adsorption kinetics compared to CaO prepared by the solid-state method. The CaO adsorbent was then combined with the Cr 2 O 3 /ZSM-5 catalyst for BFM synthesis and tested in the CO 2 –ODHP process, targeting propylene production. The BFM was extensively characterized to provide insights into the BFM’s surface chemistry, morphology, and reaction mechanism in the reactive capture process of CO 2 –ODHP. The results revealed that under isothermal adsorption–reaction conditions at 600 °C, a propane conversion of 22.5%, a propylene selectivity of 55.3%, and an olefin selectivity of 67.3% were achieved. The excellent propylene selectivity was attributed to the catalyst acidity and redox property of the Cr 2 O 3 /ZSM-5 catalyst, which facilitated the reaction pathway of propane dehydrogenation in the process of CO 2 –ODHP. Overall, this study renders Cr 2 O 3 /ZSM-5@CaO as promising BFMs with high CO 2 capture capacity and catalytic activity for integrated CO 2 capture and conversion in the ODHP reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Phosphine/Photoredox Catalyzed Anti-Markovnikov Hydroamination of Olefins with Primary Sulfonamides via α-Scission from Phosphoranyl Radicals

New strategies to access radicals from common feedstock chemicals hold the potential to broadly impact synthetic chemistry. Here, we report a dual phosphine and photoredox catalytic system that enables direct formation of sulfonamidyl radicals from primary sulfonamides. Mechanistic investigations support that the N-centered radical is generated via α-scission of the P–N bond of a phosphoranyl radical intermediate, formed by sulfonamide nucleophilic addition to a phosphine radical cation. As compared to the recently well-explored β-scission chemistry of phosphoranyl radicals, this strategy is applicable to activation of N-based nucleophiles and is catalytic in phosphine. We highlight application of this activation strategy to an intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary sulfonamides. A range of structurally diverse secondary sulfonamides can be prepared in good to excellent yields under mild conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Comprehensive Characterization of Mixed Metal Oxide Catalysts for Enhanced Catalyst Lifetime During Bio-Based C2-C6 Oxygenates to Olefins Processes (CRADA CRD-18-00728 Final Report)

Participant has developed mixed metal oxide (MMO) catalysts to selectively convert biomass-derived C2-C6 oxygenates to olefins and then hydrocarbon fuels to meet DOE 2022 fuel targets. Selective conversion ethanol to isobutylene with MMO catalysts (ZnOZrOx) requires low ethanol feeds to maintain performance. Increasing the feed results in rapid catalyst deactivation. Participant has increased catalyst stability by adding additional metal oxides. However, variations in performance based on the level and type of additive and catalytic conditions have been observed. This project will use advanced catalyst characterization methods through the ChemCatBio Advanced Catalyst Synthesis and Characterization (ACSC) project to gain insight into key catalyst features and deactivation modes with the goal of tailoring catalyst composition to improve performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A novel digital lifecycle for Material‐Process‐Microstructure‐Performance relationships of thermoplastic olefins foams manufactured via supercritical fluid assisted foam injection molding

Abstract This research significantly enhances the applicability of thermoplastic olefins (TPOs) in the automotive industry using supercritical N 2 as a physical foaming agent, effectively addressing the limitations of traditional chemical agents. It merges experimental results with simulations to establish detailed material‐process‐microstructure‐performance (MP2) relationships, targeting 5–20% weight reductions. This innovative approach labeled digital lifecycle (DLC) helps accurately predict tensile, flexural, and impact properties based on the foam microstructure, along with experimentally demonstrating improved paintability. The study combines process simulations with finite element models to develop a comprehensive digital model for accurately predicting mechanical properties. Our findings demonstrate a strong correlation between simulated and experimental data, with about a 5% error across various weight reduction targets, marking significant improvements over existing analytical models. This research highlights the efficacy of physical foaming agents in TPO enhancement and emphasizes the importance of integrating experimental and simulation methods to capture the underlying foaming mechanism to establish material‐process‐microstructure‐performance (MP2) relationships. Highlights Establishes a material‐process‐microstructure‐performance (MP2) for TPO foams Sustainably produces TPO foams using supercritical (ScF) N 2 with 20% lightweighting Shows enhanced paintability for TPO foam improved surface aesthetics Digital lifecycle (DLC) that predicts both foam microstructure and properties DLC maps process effects & microstructure onto FEA mesh for precise prediction

Engineering↗
DOE OSTI2021

Optimization of Graded Bed Reactors for Syngas to Olefin (STO) Processes

Reactor designs with mixed catalysts play an important role to transform a multiple reactor system to single-shot reactors. In addition to savings in capital and ease of implementation, single-shot reactors are useful to break equilibrium limitations, therefore increasing the yield and selectivity of desired product. However, the nonlinear, highly exothermic and poorly conditioned nature of mixed-catalyst systems makes it difficult for commercial process simulation and optimization tools to optimize these systems. Here, this study describes the zone and partial moving finite element approaches and their applications to o-xylene oxidation and syngas to olefin (STO) processes. 35% and 5% increases are achieved in the product yield for o-xylene oxidation and STO problems, respectively. Shown with these two examples, this tool is very promising in process intensification for other reactive systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Advancing Ethanol-to-Jet cost Effectiveness via direct conversion to n -Butene-Rich olefins and Co-Product Valorization

Ethanol is a promising feedstock for sustainable aviation fuel production; however, conventional routes face significant energy and cost challenges, particularly due to the ethanol dehydration step to ethylene. Here, this study leverages breakthrough experimental data to perform comprehensive techno-economic and life-cycle assessments of an innovative ethanol-to-jet process. The process employs a single-step catalytic conversion, enabled by multifunctional Cu-ZrO 2 /SBA-16 catalyst, to directly upgrade ethanol into a mixed olefin stream rich in n-butene. The single-step conversion eliminates the costly ethanol dehydration step in the conventional process. High selectivity toward n-butene offers key advantages: it simplifies downstream oligomerization into jet-range hydrocarbons and enables the co-production of renewable n-butene alongside sustainable aviation fuel. The analysis estimates a minimum fuel selling price as low as $\$$2.50 per gallon, whether using corn ethanol or cellulosic ethanol from corn stover. Life cycle CO 2 equivalent emissions are projected to be as low as 10.6 g CO 2 eq/MJ sustainable aviation fuel, representing over 70% reduction compared to conventional petroleum-based jet fuel. This one-step ethanol upgrading approach not only facilitates SAF and n-butene co-production but also provides operational flexibility. The ability to tailor product outputs allows the ethanol-to-jet process to adapt to varying feedstocks, incentive programs, and market dynamics, ultimately enhancing the economic viability of sustainable aviation fuel production.

Xu, Yiling [Pacific Northwest National Laboratory ↗
DOE OSTI2026

Kinetic model development for single step ethanol to butene rich olefin process over Cu-Y/Beta catalysts

Here, this study presents the first intrinsic kinetic model for the single-step conversion of ethanol to butene-rich olefins over bifunctional Cu-Y/Beta catalysts, addressing a critical gap in the design and scale-up of Sustainable Aviation Fuel (SAF) processes. The reaction network comprises ten global steps involving dehydrogenation, aldol condensation, hydrogenation, and dehydration reactions, distributed across Cu and rare-earth (Y) active sites. The model incorporates dual-site functionality (Cu and Y site) and explicitly accounts for key intermediates such as crotonaldehyde and butanal. Reaction rates are formulated using Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetics. Kinetic parameters are extracted by fitting the model to lab-scale packed-bed reactor data across a wide range of temperatures and space velocities, demonstrating strong agreement in ethanol conversion and product selectivity. The reaction kinetics developed in this work provide a foundational basis for constructing reactor models that enable process optimization and scale-up of ethanol-to-jet fuel technologies.

Cu-Y/Beta catalyst↗
DOE OSTI2025

Advanced Catalysts for Olefin Synthesis: Copper(II) Quinoline-Fused Oxazolidines in Alcohol Dehydration

The new copper(II) catalyst [Cu( Q FOX)- (CH 3 CN)][OTf] 2 has been synthesized and found to be active for alcohol dehydration to give olefins at 120 °C with a 1% catalyst loading ( Q FOX = di-2-quinolinyl-fused-oxazolidine). Benzylic, allylic, and tertiary alcohols are all dehydrated. In some cases, ethers are observed to be produced, but these are re-entrained into the catalytic cycle. Unactivated secondary alcohols are also dehydrated. Similar catalysts employing Mn II , Fe II , Co II , and Ni II were also synthesized but showed reduced dehydration activity compared to the copper(II) derivative. A Cu I analog was also prepared but did not show improved dehydration activity.

Alcohols↗
DOE OSTI2020

Optically Pure C 1 -Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis

An expedient access to the first optically pure ruthenium complexes containing C 1 -symmetric cyclic (alkyl)(amino)carbene (CAAC) ligands is reported. Furthermore, they demonstrate excellent catalytic performances in asymmetric olefin metathesis with high enantioselectivities (up to 92% ee). Preliminary mechanistic insights provided by DFT models highlight the origin of the enantioselectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins

Intermolecular C–C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent ‘ene’-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. Here, this active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A Mechanism-Based Reaction–Diffusion Model for Accelerated Discovery of Thermoset Resins Frontally Polymerized by Olefin Metathesis

Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers and composites. Current state-of-the-art reaction–diffusion FROMP models rely on a phenomenological description of the olefin metathesis kinetics, limiting their ability to model the governing thermo-chemical FROMP processes. Furthermore, the existing models are unable to predict the variations in FROMP kinetics with changes in the resin composition and as a result are of limited utility toward accelerated discovery of new resin formulations. In this work, we formulate a chemically meaningful model grounded in the established mechanism of ring-opening metathesis polymerization (ROMP). Our study aims to validate the hypothesis that the ROMP mechanism, applicable to monomer-initiator solutions below 100 °C, remains valid under the nonideal conditions encountered in FROMP, including ambient to >200 °C temperatures, sharp temperature gradients, and neat monomer environments. Through extensive simulations, we demonstrate that our mechanism-based model accurately predicts the FROMP behavior across various resin compositions, including polymerization front velocities and thermal characteristics (e.g., T max ). Additionally, we introduce a semi-inverse workflow that predicts FROMP behavior from a single experimental data point. Notably, the physiochemical parameters utilized in our model can be obtained through DFT calculations and minimal experiments, highlighting the model’s potential for rapid screening of new FROMP chemistries in pursuit of thermoset polymers with superior thermo-chemo-mechanical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis

Abstract Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplored. Here we report a molecular scaffold in which the rate of thermal E-to-Z isomerization of an alkene increases by a factor of as much as 10 4 in response to fast binding of a metal ion to a remote receptor site. A mechanochemical model of the olefin coupled to a compressive harmonic spring reproduces the observed acceleration quantitatively, adding the studied isomerization to the very few reactions demonstrated to be sensitive to extrinsic compressive force. The work validates experimentally the generalization of mechanochemical kinetics to compressive loads and demonstrates that the formalism of force-coupled reactivity offers a productive framework for the quantitative analysis of the molecular basis of allosteric control of reaction kinetics. Important differences in the effects of compressive vs. tensile force on the kinetic stabilities of molecules are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Cyclic olefin copolymer-based reinforced anion exchange membranes for water electrolyzers

Anion exchange membranes (AEMs) have emerged as a promising technology for water electrolysis in hydrogen production since they offer significant cost reduction in choices of electrocatalysts and bipolar plates. However, AEMs satisfying multiple requirements of high ionic conductivity, good chemical stability, robust mechanical properties, scalable synthesis, and low manufacturing costs are rare. Herein, we introduce quaternary ammonium functionalized cyclic olefin copolymers (COCs) as a new class of chemically stable and low-cost AEM materials. To further enhance the mechanical robustness, we prepared reinforced composite AEMs by impregnating the ionically functionalized COC into a mechanically robust matrix. The resulting reinforced composite membrane exhibits a high hydroxide conductivity of 127 mS cm −1 and excellent mechanical strength. In water electrolyzers, the MEA demonstrated outstanding performance, achieving a current density of 2.24 A cm −2 at 1.8 V, attributable to high conductivity, enhanced mechanical properties, and good alkaline stability of the composite membrane. These results indicate that the COC-based AEMs demonstrate good potential for application in AEM electrolyzers.

08 HYDROGEN↗
DOE OSTI2021

Identification of earth-abundant materials for selective dehydrogenation of light alkanes to olefins

Catalytic alkane dehydrogenation is of considerable importance in the synthesis of olefins industrially. However, discovery of highly active, selective, and stable heterogeneous catalysts to replace noble metal Pt remains challenging. By combining descriptor-based microkinetic modeling, high-throughput computations, machine-learning concepts, and experiments, we efficiently evaluated 1,998 bimetallic alloys and successfully identified Ni 3 Mo as one of the most promising catalysts in selective ethane dehydrogenation. This work will open new possibilities of using earth-abundant materials as catalysts for essential heterogeneous catalytic reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Conversion of Syngas and CO2 to Light Olefins using Multi-Functional Catalysts

This report describes our effort in developing a novel zeolite encapsulated metal nanoparticle catalyst for the conversion of syngas to light olefins. We have adopted a ligand assisted synthesis protocol in which first metal-amine was prepared using metal salts and suitable amine ligands. The stable metal-amine complex thus prepared was then used as the seed for the growth of zeolite in alkaline solution. We have optimized the synthesis condition as well as different amine ligand to identify the condition to obtain stable metal-amine complex. Upon synthesis of zeolite, metal particles are encapsulated inside the zeolite in a confined space. We have synthesized both Fe and Co catalyst inside silicalite and chabazite zeolite. Catalytic activity of these catalysts were evaluated for syngas conversion reaction and compared with a baseline catalyst. The activity trend of zeolite encapsulated catalyst show very different activity trend compared to the baseline catalyst. While a distribution of products with different carbon number was obtained with baseline catalyst, zeolite encapsulated catalyst show ethylene as the major product. While ~73% selectivity to C 2 -C 6 products were obtained with cahabazite encapsulated Fe catalyst, only 53% selectivity was obtained for the corresponding products with silica-alumina supported Fe catalyst. Not only higher selectivity, Fe-chabazite also produces only C 2 products (ethylene/ethane) while a distribution of products was obtained with Fe-SiAl catalyst. The significantly different reactivity associated with the chabazite encapsulated Fe catalyst was attributed to the confinement effect. We hypothesized that due to the small size of the pore, only ethylene was obtained as the product.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Integrated Carbon Capture and Propane Oxidative Dehydrogenation for Olefins Production under Isothermal Conditions over Cr₂O₃-ZSM-5/CaO-CaZrO₃ Reactive Capture Materials

Converting captured CO₂ into fuels and marketable chemicals using bifunctional materials (BFMs) represents a promising sustainable solution. In this study, a BFM composed of a Cr₂O₃/ZSM-5 catalyst and a CaO-CaZrO₃ sorbent was developed and tested for the integrated CO₂-oxidative dehydrogenation of propane (CO₂-ODHP) in a fixed bed reactor. The CaO-CaZrO₃ sorbent, prepared using the citrate sol-gel method, demonstrated high CO₂ adsorption capacity and improved cyclic stability compared to pure CaO. The BFM achieved 23.5% propane conversion, 52.5% propylene selectivity, and 68.7% olefin selectivity at isothermal adsorption-reaction conditions (630-630 °C). Overall, this study provides insights into enhancing CO2 adsorption and developing materials for integrated CO2 capture and conversion.

Baamran, Khaled↗