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Results for “Catalytic reduction”

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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

1 H NMR Quantification of Aromatic Monomers from Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) can produce high yields of aromatic monomers from lignin in native biomass. Quantification of these aromatic monomers is a well-known but demanding task, in part due to the lack of commercially available standards. Here, we demonstrate 1 H NMR spectroscopy as a complementary method to rapidly quantify aromatic monomer concentrations in RCF oils. The method exhibited good agreement with measurements from ultrahigh pressure liquid chromatography (UHPLC) for 96 RCF oils with varying monomer selectivity, with average absolute deviations of individual monomer yields between 0.5 and 1.1 wt % (relative 11–17%) and R 2 values above 0.9 compared to conventional UHPLC quantification. Quantification of S-type monomers, including for 4-ethylsyringol and 4-propenylsyringol, was generally reliable. The validity of G-type monomer quantifications depended on reaction selectivity due to overlap between peaks of 4-ethylguaiacol and 4-(3-hydroxypropyl)-guaiacol. The method could be applied on crude RCF oils without needing to perform the liquid–liquid extraction typically done for RCF reactions, thereby providing a convenient way to quantify lignin extraction and aromatic monomer yield. Overall, 1 H NMR spectroscopy can serve as a rapid primary quantification or secondary validation method for RCF monomer yield and selectivity measurements.

1H NMR spectroscopy↗
DOE OSTI2022

Multi-pass flow-through reductive catalytic fractionation

Reductive catalytic fractionation (RCF) is a promising lignin-first biorefining strategy that selectively extracts and depolymerizes lignin from whole biomass. Flow-through (FT)-RCF enables physical separation of the biomass and catalyst, but this process configuration typically operates at high solvent-to-biomass ratios. Here, we demonstrate multi-pass FT-RCF, wherein the lignin-enriched solvent obtained after an initial FT-RCF step is recycled and used in subsequent FT-RCF without intermediate lignin recovery. Multi-pass FT-RCF reduces the solvent-to-biomass ratio from 48 to 1.9 L/kg, which is a lower solvent loading than is accessible in batch reactors, without negative impacts on delignification and monomer yield with up to 12 wt % lignin in the solvent. Overall, this work demonstrates that solvent demand in RCF processes, which is a key cost and energy driver to enable this process at scale, can be reduced by recycling lignin oil between RCF reactions.

09 BIOMASS FUELS↗
DOE OSTI2024

Design and Validation of a High-Throughput Reductive Catalytic Fractionation Method

Reductive catalytic fractionation (RCF) is a promising method to extract and depolymerize lignin from biomass, and bench-scale studies have enabled considerable progress in the past decade. RCF experiments are typically conducted in pressurized batch reactors with volumes ranging between 50 and 1000 mL, limiting the throughput of these experiments to one to six reactions per day for an individual researcher. Here, we report a high-throughput RCF (HTP-RCF) method in which batch RCF reactions are conducted in 1 mL wells machined directly into Hastelloy reactor plates. The plate reactors can seal high pressures produced by organic solvents by vertically stacking multiple reactor plates, leading to a compact and modular system capable of performing 240 reactions per experiment. Using this setup, we screened solvent mixtures and catalyst loadings for hydrogen-free RCF using 50 mg poplar and 0.5 mL reaction solvent. The system of 1:1 isopropanol/methanol showed optimal monomer yields and selectivity to 4-propyl substituted monomers, and validation reactions using 75 mL batch reactors produced identical monomer yields. To accommodate the low material loadings, we then developed a workup procedure for parallel filtration, washing, and drying of samples and a 1H nuclear magnetic resonance spectroscopy method to measure the RCF oil yield without performing liquid-liquid extraction. As a demonstration of this experimental pipeline, 50 unique switchgrass samples were screened in RCF reactions in the HTP-RCF system, revealing a wide range of monomer yields (21-36%), S/G ratios (0.41-0.93), and oil yields (40-75%). These results were successfully validated by repeating RCF reactions in 75 mL batch reactors for a subset of samples. We anticipate that this approach can be used to rapidly screen substrates, catalysts, and reaction conditions in high-pressure batch reactions with higher throughput than standard batch reactors.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2025

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. Here, we demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

09 BIOMASS FUELS↗
DOE OSTI2026

Tabulated data for Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. We demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents. This is the tabulated data for the paper

biorefining↗
DOE OSTI2026

Lignin-Derived Phenolic Compounds and Water Are Effective Cosolvents for Reductive Catalytic Fractionation

Reductive catalytic fractionation (RCF) is an effective lignin-first biorefining method to extract lignin as a stabilized oil from lignocellulosic biomass. To realize RCF at scale, process modeling has shown that minimizing the use of exogenous organic solvents is critical. To this end, here we investigate the ability of lignin-derived monomers to act as either solvents or cosolvents for RCF. We begin by examining the influence of lignin-derived aromatic compounds (4-propylguaiacol, 4-propylphenol, and propylbenzene) on RCF monomer yields and subsequently extend our analysis to mixtures of 4-propylguaiacol and either methanol or water. We demonstrate that 4-propylguaiacol is an effective solvent for lignin extraction and depolymerization during RCF, especially when used in combination with water as a cosolvent. Cosolvent mixtures of 4-propylguaiacol and water enable up to 81% lignin extraction, monomer yields up to 25 wt %, and postreaction phase separation. However, unlike methanol, water as a cosolvent fails to inhibit aromatic ring hydrogenation when conducted over Ru/C as a catalyst, potentially leading to excess hydrogen consumption in a process utilizing this approach. Nonetheless, these results suggest a promising strategy for eliminating external organic solvents from RCF by utilizing mixtures of lignin-derived compounds and water as alternative extraction solvents.

biorefining↗
DOE OSTI2020

The Catalytic Reduction of Dinitrogen Under Mild Conditions (Final Report)

In order to use molecular hydrogen as an alternative to fossil fuels, large quantities of hydrogen (or protons and electrons) would have to be generated from water using a method based on solar energy and stored as a molecule in which hydrogen is a high weight percentage. The hydrogen must then be generated as needed from the form in which it is stored. An attractive molecule for this purpose is ammonia (~17% hydrogen by weight). Among the many problems that must be addressed for a successful implementation of this approach in the long term is the reduction of nitrogen catalytically to ammonia with protons and electrons under mild conditions, a goal that is addressed in this proposal. The first abiological catalytic reduction of N 2 to NH 3 by protons and electrons under mild conditions (22 °C and 1 atm) employed molybdenum catalysts, [(HIPTNCH 2 CH 2 ) 3 N]Mo (HIPTN 3 N 3- ), where HIPT (hexaisopropylterphenyl) is 3,5- (2,4,6-i-Pr 3 C 6 H 2 ) 2 C 6 H 3 . A total of approximately four turnovers (to give a maximum of eight equivalents of ammonia) along with approximately one equivalent of hydrogen per N 2 reduced, were found. A limitation of this catalytic approach is loss of the ligand from the metal. This project is aimed at developing a complex that contains a ligand that will not be removed from the metal. A macrocyclic TREN-based ligand of this type has been synthesized recently. The project is aimed at making similar ligands and molybdenum complexes that contain them and testing the new catalysts for catalytic reduction of dinitrogen. The results of these investigations will help guide further design of ligands for more efficient reduction of nitrogen to ammonia and ultimately an integrated device in which protons and electrons are generated using solar energy and employed to reduce nitrogen to ammonia using molybdenum catalysts.

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

Recent advances in hybrid metal oxide–zeolite catalysts for low-temperature selective catalytic reduction of NOx by ammonia

A hybrid catalytic system comprised of metal oxide and Cu or Fe exchanged zeolite components represents a potential advancement of state-of-the-art for selective catalytic reduction (SCR) of NOx by ammonia, including an elegant solution to the current challenge of improving the low-temperature efficiency of SCR catalysts. The idea is to enable in-situ NO oxidation over metal oxide component and concomitant fast SCR over zeolite component in the so-called “bifunctional mechanism”. This review is presented in the wake of growing interest in this innovative catalytic system. We begin this review by presenting key parameters that contribute to the synergy between metal oxide and zeolite components. Then, we discuss the materials selection for both components and their possible interactions in the system, followed by a summary of recent NH3-SCR investigations over multiple metal oxide–zeolite pairs and additional discussion on pairing techniques potentially explorable in upcoming studies. Finally, we end the review by providing the perspectives on future challenges in the development of this catalytic system.

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

Catalytic Reduction of Cyanide to Ammonia and Methane at a Mononuclear Fe Site

Nitrogenase enzymes catalyze nitrogen reduction (N 2 R) to ammonia and also the reduction of non-native substrates, including the 7H + /6e – reduction of cyanide to CH 4 and NH 3 . CN – and N 2 are isoelectronic, and it is hence fascinating to compare the mechanisms of synthetic Fe catalysts capable of both CN – and N 2 reduction. Here, we describe the catalytic reduction of CN – to NH 3 and CH 4 by a highly selective (P 3 Si )Fe(CN) catalyst (P 3 Si represents a tris(phosphine)silyl ligand). Catalysis is driven in the presence of excess acid ([Ph 2 NH 2 ]OTf) and reductant ((C 6 H 6 ) 2 Cr), with turnover as high as 73 demonstrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Investigation of catalytic reduction and filter techniques for simultaneous measurements of NO, NO2, and HNO3 in the stratosphere

A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

Wendt, J.↗
DOE OSTI2021

Lithium cuprate, a multifunctional material for NO selective catalytic reduction by CO with subsequent carbon oxide capture at moderate temperatures

Li 2 CuO 2 was evaluated as a possible catalyst for the NO selective catalytic reduction (NO SCR) by CO. The initial idea was supported by ab initio thermodynamic analysis. This analysis showed that NO SCR was favored by using Li 2 CuO 2 as a catalyst, based on the calculated heat of reaction and Gibbs free energy. The NO SCR reaction was evaluated under dynamic, isothermal and cyclic conditions using different NO : CO ratios (2 : 1, 1 : 1 and 1 : 2). The dynamic and isothermal experiments showed that Li 2 CuO 2 does reduce NO in the presence of CO to reach higher conversions (>90%) between 400 and 450 °C. However, it must be mentioned that the catalytic process was reduced once some of the produced CO 2 was captured on the ceramic. At that point, Li 2 CuO 2 acts as a bifunctional material, catalyzing the NO SCR reaction and capturing some of the produced CO 2 . Moreover, cyclic experiments evidenced high NO reduction. Finally, a different set of experiments showed that this catalytic reduction performed differently if NO and CO were previously fed. Finally, when lithium cuprate is previously carbonated (initial CO feed), the catalytic reaction does not complete. In contrast, when there was a previous nitrate formation (initial NO feed), the reaction reached 100% efficiency.

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

Insights into palladium poisoning of Cu/SSZ-13 selective catalytic reduction catalysts

Here, the impacts of Pd poisoning to the activity, selectivity, and hydrothermal stability of Cu/SSZ-13 selective catalytic reduction (SCR) catalysts are reported. Pd lowers DeNOx efficiency of Cu/SSZ-13 via two mechanisms: (1) displacing SCR active sites in the form of isolated Pd-ions, and (2) catalyzing non-selective NH 3 oxidation in the form of PdO. The first mechanism works by the diffusion of isolated Pd-ions into chabazite cages to displace ZCu II OH SCR active species, and it occurs on Cu/SSZ-13 catalysts with and without external surface CuO clusters in similar fashion. In contrast, the second mechanism works differently with and without external surface CuO clusters. For Cu/SSZ-13 catalyst without external CuO clusters (i.e., primarily isolated Cu-ions), PdO leads to significant decrease of DeNOx efficiency at reaction temperatures above ~400°C due to its non-selective NH 3 oxidation activity at high temperatures. However, this poisoning effect becomes much less impactful on Cu/SSZ-13 catalyst containing CuO clusters. This is due to the formation of CuO-PdO solid solution via interactions between CuO and PdO, which reduces non-selective NH 3 oxidation potential. Furthermore, this solid solution formation even mitigates adverse effects caused by hydrothermal aging. Hence, the poisoning effects of Pd are closely related to Cu speciation and spatial distribution of a Cu/SSZ-13 catalyst. Finally, this study suggests a strategy in eliminating Pd poisoning, that is, the introduction of an oxide phase that effectively traps PdO but does not adversely influence SCR.

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

Quantitative Cu Counting Methodologies for Cu/SSZ-13 Selective Catalytic Reduction Catalysts by Electron Paramagnetic Resonance Spectroscopy

Here, two Cu/SSZ-13 selective catalytic reduction (SCR) catalysts with distinct Si/Al ratios and isolated Z2Cu and ZCuOH distributions are prepared for in situ electron paramagnetic resonance (EPR) spectroscopic studies. These in situ studies include dehydration, titration of dehydrated samples with NO+O 2 and NH 3 , titration of NH 3 saturated samples with NO+O 2 , and finally steady-state standard NH 3 -SCR reaction. During dehydration, EPR active hydrated ZCuOH loses H 2 O ligands and becomes EPR silent due to a pseudo Jahn-Teller effect; a portion of ZCuOH also undergoes autoreduction to ZCu(I) species, a process that also induces EPR invisibility. During NO+O 2 treatment of dehydrated samples, ZCu(I) species are oxidized to Cu(II)-NO 3 - species, regaining EPR visibility. During NH3 titration, EPR silent dehydrated ZCuOH can also regain EPR visibility by coordinating with NH 3 ligands. During NO+O 2 titration of NH 3 -saturated samples, EPR active Cu contents first decrease due to Cu(II) reduction to Cu(I), and then increase due to Cu(II)-NO 3 - species formation. However, the Cu(II)-NO 3 - formation chemistry is substantially slower for the Si/Al = 36 catalyst. In steady-state SCR studies, the EPR active content decreases with increasing temperature in the kinetically controlled low-temperature regime and becomes largely invariant in mass-transfer limited regime. Importantly, Cu sites in the SCR more active Si/Al = 6 catalyst display substantially higher EPR visibility than the SCR less active Si/Al = 36 catalyst at any reaction temperatures tested. The higher Cu loading for the former catalyst is believed to be key for this difference.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗