Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Adsorbent”

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 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Method for direct conversion of carbon dioxide to dialkyl carbonates using ethylene oxide as feedstock

A method for co-production of high purity dimethyl carbonate and mono-ethylene glycol by applying a reactor, such as a membrane reactor and/or an adsorbent-catalytic reactor by capturing and reacting carbon dioxide with methanol and ethylene oxide. Carbon dioxide may be recovered from primary sources (utilities and industrial processes) by a membrane or solid adsorbent, and subsequently converted to an intermediate hydroxy-ethyl-methyl carbonate by reacting with ethylene oxide and methanol. For high-purity carbon dioxide (obtained by carbon capture technologies or from an ethanol fermentation process), the membrane reactor is replaced with a catalytic reactor for direct conversion of carbon dioxide to hydroxy-ethyl-methyl carbonate by reacting with ethylene oxide and methanol. The hydro-ethyl-methyl carbonate is further reacted with methanol for conversion to dimethyl carbonate. A combination of heterogeneous and homogeneous catalysts is implemented for an effective conversion of carbon dioxide. An integrated reactive distillation process using side reactors is used for facilitating catalytic reaction for production of high purity dimethyl carbonate.

Panchal, Chandrakant B.↗
DOE OSTI2021

Decontamination of tritiated water

Methods and systems directed to the separation of tritium from an aqueous stream are described. The separation method is a multi-stage method that includes a first stage during which tritium of a tritium-contaminated aqueous stream is adsorbed onto a separation phase, a second stage during which the adsorbed tritium is exchanged with hydrogen in a gaseous stream to provide a gaseous stream with a high tritium concentration, and a third stage during which the tritium of the gaseous stream is separated from the gaseous stream as a gaseous tritium product.

Xiao, Xin↗
DOE OSTI2022

Amine-appended metal-organic frameworks exhibiting a new adsorption mechanism for carbon dioxide separations

An adsorption material is disclosed that comprises a metal-organic framework and a plurality of ligands. The metal-organic framework comprising a plurality of metal ions. Each respective ligand in the plurality of ligands is amine appended to a respective metal ion in the plurality of metal ions of the metal-organic framework. Each respective ligand in the plurality of ligands comprises a substituted 1,3-propanediamine. The adsorbent has a CO 2 adsorption capacity of greater than 2.50 mmol/g at 150 mbar CO 2 at 40° C. Moreover, the adsorbent is configured to regenerate at less than 120° C. An example ligand is diamine 2,2-dimethyl-1,3-propanediamine. An example of the metal-organic framework is Mg 2 (dobpdc), where dobpdc 4− is 4,4′-dioxidobiphenyl-3,3′-dicarboxylate. Example applications for the adsorption material are removal of carbon dioxide from flue gas and biogasses.

Long, Jeffrey R.↗
DOE OSTI2023

Compositions for carbon dioxide separation using steam regeneration, and method for preparing same

Compositions and methods of preparing the compositions are disclosed for sorbents and other surfaces that can adsorb and desorb carbon dioxide. A sorbent or surface can include a metal compound such as an alkali or alkaline earth compound and a support. The sorbent can be prepared by several methods, including an incipient wetness technique. The sorbents have a CO 2 adsorption and desorption profile. A sorbent having high levels of a metal compound and adsorbed CO 2 is disclosed.

Elliott, Jeannine Elizabeth↗
DOE OSTI2020

Computational modeling predicts the stability of both Pd + and Pd2 + ion-exchanged into H-CHA

Passive NO x adsorbers (PNA) using Pd/zeolites have emerged as a promising solution for the reduction of cold-start emissions from vehicle exhaust. However, the nature of the active sites and the mechanisms underlying NO x adsorption in Pd/zeolites remain a subject of ongoing investigation. In this study, we employ quantum chemical simulations to investigate the structure of Pd species in cation-exchange sites at isolated Al and Al pairs in the 6-ring and 8-ring of the CHA framework before the introduction of NO x . Our calculations show that the speciation of Pd in these exchange sites strongly depends on the precise Al arrangement within the framework, as well as the operating conditions. Ionically dispersed Pd is found to be the most favorable species over a wide range of oxidizing and reducing conditions. Small oligomers of PdO and metallic Pd do not appear to be competitive at either isolated Al or Al pairs. Notably, our calculations show that ion exchange sites other than next–next–nearest neighbor Al pairs in the 6-ring will be preferentially occupied by Pd + instead of Pd 2+ . The stability of Pd + in the zeolite environment is an interesting contrast with its rareness in molecular Pd compounds. Nonetheless, a detailed analysis of the electronic structure shows that predicted Pd oxidation states are consistent with chemical intuition for all complexes investigated in this study. We also discuss the potential ambiguity in Pd characterization provided by typical experimental techniques such as XANES, EXAFS and UV-Vis, and highlight the need for additional EPR spectroscopy studies to further elucidate the initial Pd speciation in zeolites for PNA applications.

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

Estimation of isosteric heat of adsorption from generalized Langmuir isotherm

Simulation and design of adsorptive separation units demand accurate estimation of thermodynamic properties. Isosteric heat of adsorption as calculated from generalized Langmuir (gL) isotherm coupled with Clausius-Clapeyron expression for pure component and mixed-gas adsorption equilibria is presented in this work. The estimated isosteric heat of adsorption as functions of surface loading and composition is validated against the experimental data for various adsorption systems. Furthermore, the gL results are compared against classical Langmuir (cL) and Toth isotherm for pure components and with Ideal Adsorbed Solution Theory (IAST) for mixed-gas adsorption equilibria. Furthermore, the comparison highlights that gL outperforms cL and Toth for pure component adsorption and IAST for mixed-gas adsorption, and gL reliably captures the loading dependence and the composition dependence for isosteric heat of adsorption.

42 ENGINEERING↗
DOE OSTI2020

The superior hydrothermal stability of Pd/SSZ-39 in low temperature passive NOx adsorption (PNA) and methane combustion

We successfully synthesized uniform SSZ-39 with an average crystal size of about a micron. Pd (0.7 - 3 wt%) was supported on SSZ-39 with Si/Al ratio ~12. The as-synthesized materials were characterized by FTIR, XRD, Helium Ion Microscopy, HAADF-STEM imaging, 27 Al, 29 Si and H solid state NMR spectroscopic techniques. FTIR studies with CO and NO probe molecules reveal that the 0.7 wt% Pd/SSZ-39 material with Si/Al ~12 has the majority of Pd dispersed atomically as isolated Pd(II) and Pd(II)-OH centers, and thus can be used as a low-temperature passive NOx adsorber. Pd(II)-NO, Pd(II)(OH)(NO) and Pd(II)(CO)(NO) complexes form during PNA in this material. We compare this PNA material directly with the Pd/SSZ-13 system (with Si/Al ratio ~12) and show its superior hydrothermal stability. Remarkably, Pd/SSZ-39 with Si/Al ratio ~12 survives hydrothermal aging up to 815 ºC in 10% H 2 O/Air vapor for 16 hours without significant loss in activity. The SSZ-39 crystal structure remains intact during hydrothermal aging up to 1,000 ºC as we elucidate it with XRD and HAADF-STEM imaging/EDS mapping. However, changes to the framework during such harsh hydrothermal treatment significantly change the NOx release profiles during PNA as evidenced by high-field 27 Al NMR on fresh and aged Pd/SSZ-39 samples as well as PNA performance measurements. Besides PNA application, these hydrothermally very stable materials (3 wt% Pd on SSZ-39 with Si/Al ratio ~12) can be used as a robust methane combustion catalyst under industrially relevant conditions (GHSV~600,000hr -1 ). This catalyst shows minimal deactivation after both harsh hydrothermal aging at 750 and 800 ºC, and prolonged time on stream (105 hrs) at 425 °C. In contrast, both 3wt% Pd/alumina and 3wt% SSZ-13 supported samples lose a significant portion of their activity. Our study opens new avenues to prepare the most hydrothermally stable known Pd/zeolite materials with applications for adsorption and catalytic hydrocarbon combustion under industrially relevant conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Unusual water-assisted NO adsorption over Pd/FER calcined at high temperatures: The effect of cation migration

Moisture contained in vehicle exhaust gas normally degrades the capacity and efficiency of Pd ion-exchanged zeolites as NO x adsorbents by competitive adsorption on active sites. Here, we report a counterexample to this general proposition, in which moisture facilitates the storage of NO as a nitrosyl complex on hydrated Pd ions in high temperature calcined FER-type zeolites. The divalent Pd 2+ cations upon elevated temperature (>800 °C) calcination occupy cationic position that render them fully coordinated by oxygen ions of the zeolite framework, and become inactive for the adsorption of probe molecules such as NO or CO. These ‘hidden’ Pd ions, however, are accessible by NO when the zeolite is hydrated, but readily release NO at around 200°C as dehydration proceeds. Herein, by combining systematic in situ infra-red data with X-ray diffraction Rietveld analyses, we revealed that the high temperature-induced relocation of Pd ions to more stable cationic positions located near 6-membered ring of the ferrierite cage is responsible for this anomalous behavior. This discovery constitutes a notable advance in understanding coordination chemistry of cations in zeolites.

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

A new hypothesis for air loss in cement systems containing fly ash

Although there are many benefits gained from incorporating fly ash into concrete, carbon contamination in the fly ash has been shown to interfere with the efficacy of organic additives in an unpredictable manner. This work uses surface tension measurements to quantify the adsorption of air-entraining agents (AEA) onto cement and fly ash. Both the adsorption capacity of the adsorbents and the adsorption isotherms indicate that the fly ash particles, rather than the carbon itself, dominate adsorption in a carbon-contaminated ash in cement pore solution. We propose that adsorption onto fly ash particles and cement actually improve air entrainment via Pickering stabilization. While the carbon is still expected to contribute to air loss via hydrophobic adsorption of the surfactants, we suggest that the primary way in which the carbon interferes is by shielding surfactant-coated fly ash particles from participating in air development and Pickering stabilization during mixing.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Influence of elevated temperature and oxygen on the capture of radioactive iodine by silver functionalized silica aerogel

Reprocessing is considered a competent strategy for spent nuclear fuel management, yet radioiodine ( 129 I) is emitted in reprocessing off-gas as a hazardous byproduct. Silver functionalized silica aerogel (Ag 0 -aerogel), a promising iodine capture material, experiences a reduction in its capacity after prolonged exposure to off-gas components at elevated temperatures, a phenomenon termed as aging. To fully understand this process, we isolated the contribution of each aging factor, exposing Ag 0 -aerogel samples to N 2 and dry air gas streams, respectively, at 150 °C for different time periods. Aged samples were loaded with I 2 to examine the capacity change and comprehensively characterized to investigate the evolution of their properties. Results show that temperature alone did not alter Ag 0 -aerogel's capacity but triggered Ag 0 nanoparticles sintering and generated organic sulfur species. The presence of O 2 reduced the capacity by ~20 %, causing (i) formation of silver sulfide (Ag 2 S) crystals and (ii) oxidation of Ag-thiolate (Ag-S-r) to Ag sulfonate (Ag-SO 3 -r). Given that Ag 2 S readily adsorbs I 2 , the formation of Ag-SO 3 -r is the major inhibitor for iodine adsorption. This hypothesis was supported by density functional theory (DFT) simulations. These findings unraveled key mechanisms of Ag 0 -aerogel aging, which are useful in the development of materials that withstand realistic spent-nuclear-fuel-reprocessing off-gas conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Metal Independent Correlations for Site-specific Binding Energies of Relevant Catalytic Intermediates

Establishing energy correlations among different metals can accelerate the discovery of efficient and cost-effective catalysts for complex reactions. Using a recently introduced coordination-based model, we can predict site specific metal binding energies (∆EM) that can be used as a descriptor for chemical reactions. In this study, we have examined a range of metals including Ag, Au, Co, Cu, Ir, Ni, Os, Pd, Pt, Rh, and Ru and found linear correlations between predicted ∆EM and adsorption energies of CH and O (∆ECH and ∆EO) at various coordination environment for all the considered metals. Interestingly, all the metals correlate with one another under specific surface site coordination, indicating that different metals are interrelated in a particular coordination environment. Furthermore, we have tested and verified for PtPd and PtIr-based alloys that they follow a similar behavior. Moreover, we have expanded the metal space by taking some early transition metals along with few s-block metals and shown a cyclic behavior of the adsorbate binding energy (∆EA) versus ∆EM. Therefore, ∆ECH and ∆EO can be efficiently interpolated between metals, alloys and intermetallics based on information related to one metal only. This simplifies the process of screening new metal catalyst formulations and their reaction energies.

Density function theory↗
DOE OSTI2021

Imaging Reconfigurable Molecular Concentration on a Graphene Field-Effect Transistor

The spatial arrangement of adsorbates deposited onto a clean surface under vacuum typically cannot be reversibly tuned. Here we use scanning tunneling microscopy to demonstrate that molecules deposited onto graphene field-effect transistors (FETs) exhibit reversible, electrically tunable surface concentration. Continuous gate-tunable control over the surface concentration of charged F 4 TCNQ molecules was achieved on a graphene FET at T = 4.5K. This capability enables the precisely controlled impurity doping of graphene devices and also provides a new method for determining molecular energy level alignment based on the gate-dependence of molecular concentration. Gate-tunable molecular concentration is explained by a dynamical molecular rearrangement process that reduces total electronic energy by maintaining Fermi level pinning in the device substrate. Finally, the molecular surface concentration is fully determined by the device back-gate voltage, its geometric capacitance, and the energy difference between the graphene Dirac point and the molecular LUMO level.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Unifying thermochemistry concepts in computational heterogeneous catalysis

Thermophysical properties of adsorbates and gas-phase species define the free energy landscape of heterogeneously catalyzed processes and are pivotal for an atomistic understanding of the catalyst performance. These thermophysical properties, such as the free energy or the enthalpy, are typically derived from density functional theory (DFT) calculations. Enthalpies are species-interdependent properties that are only meaningful when referenced to other species. The widespread use of DFT has led to a proliferation of new energetic data in the literature and databases. However, there is a lack of consistency in how DFT data is referenced and how the associated enthalpies or free energies are stored and reported, leading to challenges in reproducing or utilizing the results of prior work. Additionally, DFT suffers from exchange–correlation errors that often require corrections to align the data with other global thermochemical networks, which are not always clearly documented or explained. In this review, we introduce a set of consistent terminology and definitions, review existing approaches, and unify the techniques using the framework of linear algebra. This set of terminology and tools facilitates the correction and alignment of energies between different data formats and sources, promoting the sharing and reuse of ab initio data. Standardization of thermochemistry concepts in computational heterogeneous catalysis reduces computational cost and enhances fundamental understanding of catalytic processes, which will accelerate the computational design of optimally performing catalysts.

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

Adsorptive denitrogenation of model fuel with silica gel

The results establish the adsorption capacity, kinetics, interaction strength of pyridine/indole with sorbents and regeneration, highlighting silica gel's potential as an efficient and cost-effective adsorbent for biofuel nitrogen compounds removal.

09 BIOMASS FUELS↗
DOE OSTI2026

Waste to worth: a circular solution through lignin engineering

The inefficient management of industrial waste threatens environmental sustainability, requiring scalable resource recovery solutions. To address these challenges, we propose a novel and sustainable in-situ one-step strategy for the simultaneous recovery and functionalization of lignin from industrial black liquor, using a sustainable organic acid system assisted by choline chloride. The functionalized lignin adsorbent material (FLAM) exhibited superior adsorption performance, effectively treating animal feedlot wastewater to recover ammonia. The ammonia enriched FLAM was subsequently repurposed as a slow-release fertilizer, enhancing plant growth and demonstrating a closed-loop pathway for waste valorization and nutrient recycling. Methylene blue was used as a model cationic compound to simulate the adsorption behavior and interactions. FLAM achieved a high adsorption capacity of 725.98 mg/g across a broad pH range, significantly outperforming commercial kraft lignin. This sustainable approach advances circular economy principles by integrating remediation and resource recovery, offering a scalable, eco-friendly solution for environmental applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Toluene Adsorption and TPD

Raw data for toluene adsorption and TPD experiments on two different adsorbents using a custom flow-through, bench-top reactor capable of controlling gas compositions and temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Engineering Study of Svante’s Solid Sorbent Post-Combustion CO 2 Capture Technology at a Linde Steam Methane Reforming H 2 Plant

An initial engineering design study was performed for an advanced post combustion CO 2 capture (PCC) technology to be installed at a commercial-scale steam methane reforming (SMR) hydrogen plant located in the US Gulf Coast. The PCC process integrated the VeloxoTherm™ structured adsorbent technology from Svante for the CO 2 separation and CO 2 compression and purification and balance of plant systems provided by Linde. This pre-FEED equivalent study included following: (1) design basis, (2) basic engineering, including development of process flow diagrams and heat & material balances, (3) inside the battery limit (ISBL) equipment and systems specification, (4) balance of plant outside the battery limit (OSBL) equipment and systems specifications, (5) technology maturation plan, (6) hazard identification (HAZID) review, (7) environmental, health and safety (EH&S) assessment and environmental permitting analysis, (8) constructability review, (9) ISBL and OSBL EPC cost estimation, and (10) commercial-scale techno-economic analysis including capital expenditures (CAPEX) and operating expenditures (OPEX) and CO 2 capture cost estimates.

03 NATURAL GAS↗
DOE OSTI2021

Analysis of Ion-Exchanged ZSM-5, BEA, and SSZ-13 Zeolite Trapping Materials under Realistic Exhaust Conditions

An industry-defined evaluation protocol was used to evaluate the hydrocarbon trapping (HCT) and passive NOx adsorption (PNA) potential for BEA, ZSM-5, and SSZ-13 zeolites with ion-exchanged Pd or Ag. All materials underwent 700 °C degreening prior to exposure to an industry-derived protocol gas stream, which included NOx, ethylene, toluene, and decane as measured trapping species as well as common exhaust gasses CO, H2O, O2, CO2, and H2. Evaluation showed that BEA and ZSM-5 zeolites were effective at trapping hydrocarbons (HCs), as saturation was not achieved after 30 min of exposure. SSZ-13 also stored HCs but was only able to adsorb 20–25% compared to BEA and ZSM-5. The presence of Ag or Pd did not impact the overall HC uptake, particularly in the first three minutes. Pd/zeolites had significantly lower THC release temperature, and it aided in the conversion of the released HCs; Ag only had a moderate effect in both areas. With respect to NOx adsorption, the level of uptake was much lower than HCs on all samples, and Ag or Pd was necessary with Pd being notably more effective. Additionally, only Pd/ZSM-5 and Pd/SSZ-13 continue to store a portion of the NOx above 200 °C, which is critical for downstream selective catalytic NOx reduction (SCR). Hydrothermal aging (800 °C for 50 h) of a subset of the samples were performed: BEA, Pd/BEA, ZSM-5, Pd/ZSM-5, and Pd/SSZ-13. There was a minimal effect on the HC storage, ~10% reduction in capacity with no effect on release temperature; however, only Pd/SSZ-13 showed significant NOx storage after aging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗