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At least 19 records

Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides

Electrochemical regeneration of organic hydrides is often hindered by the rapid dimerization of organic radicals produced as the first intermediates of these electrochemical transformations. Here, we utilize proton-coupled electron transfer to outcompete the undesired dimerization and achieve successful hydride regenerations of two groups of organic hydrides – acridines and benzimidazoles. An analysis of the critical factors that control the regeneration pathways of organic hydrides is demonstrated in this report.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil

We assessed molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60-h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt% and 0.01 mg KOH g-1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60-h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are promising catalytic materials which could lead to a significant cost reduction in hydroprocessing bio-oils. This paper highlights areas for future research which will be needed to further understand carbide structure-function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.

Choi, Jae-Soon↗

Trace Contaminant Control Test Bed for Evaluation of TCC Prototypes with Vacuum Regenerable and Non-Regenerable Sorbents

A new Space Suit Exploration Portable Life Support System (xPLSS) is being designed, built, integrated, and tested into the Extra-Vehicular Mobility Unit (xEMU). The Trace Contaminant Control (TCC) system is a component in the oxygen ventilation loop of xPLSS that removes contaminants generated by the crewmembers’ metabolic processes. The primary trace contaminants that must be removed include ammonia (NH3), carbon monoxide (CO), formaldehyde (CH2O), and methyl mercaptan (CH3SH). The current state-of-the-art TCC sorbent is non-regenerable activated carbon. As a non-regenerable sorbent, its use negatively impacts the logistics for future missions. Thus, an ideal solution can be a vacuum-regenerable sorbent integrated with the xPLSS CO2/H2O removal system. To test new designs and sorbents, XploSafe has constructed a recirculating test bed that mimics the environment within the xPLSS by providing concentrations of the trace contaminant analytes generated at the operating temperature, humidity, pressure, and flow rates of the xPLSS. This system can perform regeneration or desorption by exposing the sorbent to a pressure swing from 4.3 psia to <1 torr over approximately 2 minutes. Using this test system, XploSafe evaluated various TCC prototypes constructed using rapid prototyping techniques and identified a process that allows vacuum regenerative TCC designs to be quickly examined for flow, pressure drop, and performance. By using toluene as a segregate for volatile organics, this test system was evaluated using both vacuum regenerable and non-regenerable sorbents to demonstrate the operational effectiveness of these sorbents in maintaining the concentrations of the trace contaminant analytes below the 7-day Spacecraft Maximum Allowable Concentrations.

Nicholas Materer↗

Bosch Carbon Catalyst Regeneration in Water II: Analysis of Bosch Catalyst Beads Throughout the Initial Regeneration Process

Catalyst integrity is an important factor in reactor longevity since it changes the effectiveness of a reaction. A Carbon Formation Reactor (CFR), used within Series Bosch (S-Bosch), utilizes an iron alloy catalyst to convert carbon monoxide and hydrogen into water and solid carbon. The catalyst promotes the formation of carbon to such an extent that pressure-causing clogs form within the reactor and reaction sites on the catalyst become limited. To remove carbon from both the reactor and the surface of the iron alloy catalyst, a technique was developed that utilizes water, an In-Situ Resource Utilization (ISRU) Resource, and agitation to regenerate the reactor. To ascertain catalyst integrity throughout this regenerative process, sample catalyst beads were taken before and after the carbon formation reaction, and then after the regeneration process. Additionally, wastewater from the regeneration process was sampled. The sampled beads and wastewater were observed under a Scanning Electron Microscopy (SEM) microscope and the beads were chemically etched to determine if the catalyst had degraded at any point during this process, and if catalyst was lost. Minimal catalyst degradation was observed after carbon formation in the CFR.

regeneration↗

Bosch Carbon Catalyst Regeneration in Water II: Analysis of Bosch Catalyst Beads Throughout the Initial Regeneration Process

Catalyst integrity is an important factor in reactor longevity since it changes the effectiveness of a reaction. A Carbon Formation Reactor (CFR), used within Series Bosch (S-Bosch), utilizes an iron alloy catalyst to convert carbon monoxide and hydrogen into water and solid carbon. The catalyst promotes the formation of carbon to such an extent that pressure-causing clogs form within the reactor and reaction sites on the catalyst become limited. To remove carbon from both the reactor and the surface of the iron alloy catalyst, a technique was developed that utilizes water, an In-Situ Resource Utilization (ISRU) Resource, and agitation to regenerate the reactor. To ascertain catalyst integrity throughout this regenerative process, sample catalyst beads were taken before and after the carbon formation reaction, and then after the regeneration process. Additionally, wastewater from the regeneration process was sampled. The sampled beads and wastewater were observed under a Scanning Electron Microscopy (SEM) microscope and the beads were chemically etched to determine if the catalyst had degraded at any point during this process, and if catalyst was lost. Minimal catalyst degradation was observed after carbon formation in the CFR.

Series Bosch↗

Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Abstract Ceria (CeO 2 ) supports are unique in their ability to trap ionic platinum (Pt), providing exceptional stability for isolated single atoms of Pt. The reactivity and stability of single‐atom Pt species was explored for the industrially important light alkane dehydrogenation reaction. The single‐atom Pt/CeO 2 catalysts are stable during propane dehydrogenation, but are not selective for propylene. DFT calculations show strong adsorption of the olefin produced, leading to further unwanted reactions. In contrast, when tin (Sn) is added to CeO 2 , the single‐atom Pt catalyst undergoes an activation phase where it transforms into Pt–Sn clusters under reaction conditions. Formation of small Pt–Sn clusters allows the catalyst to achieve high selectivity towards propylene because of facile desorption of the product. The CeO 2 ‐supported Pt–Sn clusters are very stable, even during extended reaction at 680 °C. Coke formation is almost completely suppressed by adding water vapor to the feed. Furthermore, upon oxidation the Pt–Sn clusters readily revert to the atomically dispersed species on CeO 2 , making Pt–Sn/CeO 2 a fully regenerable catalyst.

Xiong, Haifeng↗

Regeneration efficiency, shuttle heat loss and thermal conductivity in epoxy-composite annualr gap regenerators from 4K to 80K

A test apparatus designed to simulate a section of a Stirling cycle cryocooler was built. Measurements of regeneration efficiency, shuttle heat loss and thermal conductivity reported for several regenerator test sections. The test composites were epoxy glass, epoxy glass with lead particles, epoxy glass with activated charcoal and epoxy graphite. Losses measured for these materials were approximately the same. Losses are in good agreement with those calculated theoretically for an epoxy glass (C-10) composite. The implications of these results on cryocooler design are discussed.

Myrtle, K.↗

Regenerable hydrogen chloride removal sorbent and regenerable multi-functional hydrogen sulfide and hydrogen chloride removal sorbent for high temperature gas streams

A novel regenerable composition for removing hydrogen chloride and hydrogen sulfide from a gas stream, the sorbent comprising a mixture containing from about 5 wt % manganese oxide to about 99 wt. % manganese oxides where manganese can exist in various oxidation states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust foil regenerator flow loss and heat transfer tests under oscillating flow condition

A regenerator works as an energy storage component in a Stirling engine. Thus, it is one of the most critical components that makes the Stirling engine highly efficient. Traditionally, the regenerators are made of wire media such as woven screens and random fibers. These wire regenerators experience considerably high flow losses through the regenerator due to the flow separation and the resulting vortices. The high flow losses associated with the flow separation and vortices result in a lower engine efficiency. This research is to test a new robust foil regenerator to investigate its feasibility for free-piston Stirling engine applications. The robust foil regenerator is configured with parallel flow channels and stiffening ribs. Comparing to complex flows patterns in woven screen and random fiber regenerators, the flows in the parallel plates are simple and the flow losses are considerably small, and the heat transfer coefficient is also relatively small. To test the regenerator experimentally, a regenerator test rig was manufactured. To verify the accuracy of the test rig, a woven screen regenerator was made and tested prior to the robust foil regenerator test. The friction factor correlation of the woven screen regenerator shows a good agreement with the published regenerator correlations. The robust foil regenerator tests were conducted under the oscillating flow condition with different Reynolds numbers. The flow losses were measured with dynamic pressure transducers and the friction coefficient was derived from measured pressure drop. The measured temperature difference over the regenerator was used to calculate the heat transfer coefficient and Nusselt number. The figure of merit with two methods of NPH/NTU ratio and j/f ratio was calculated to evaluate the suitability of the robust foil regenerator. The results show that the robust foil regenerator has considerably higher figure of merit and therefore, better performance than other types of regenerator.

42 ENGINEERING↗

Restoring ZSM-5 performance for catalytic fast pyrolysis of biomass: Effect of regeneration temperature

Zeolite catalysts used for biomass catalytic fast pyrolysis (CFP) deactivate rapidly, similar to a fluidized catalytic cracking (FCC) catalyst used in refining. To operate effectively when there is rapid deactivation, biomass CFP can take place in a riser FCC-style reactor in which the catalyst has a short contact time (seconds) with reactants before it is regenerated. The regeneration, therefore, has two major needs for effective operation: 1) heat balance, since the heat required for the CFP reactions is brought into the reactor by the hot catalyst and 2) relatively short (minutes) regeneration to restore the catalyst activity to be near its initial state. In order to understand effective conditions to regenerate zeolites used for CFP, a series of experiments were performed to determine the effect of regeneration temperature on the activity of ZSM-5 (SiO 2 /Al 2 O 3 = 30). After use for pine pyrolysis vapor upgrading, the catalyst was oxidized in 4% O 2 at temperatures between 500-700 °C and reevaluated for the upgrading of pine pyrolysis vapors to assess the extent of regeneration. Additional testing was performed using ethylene aromatization as a surrogate reaction to probe regeneration efficiency. Regeneration experiments were performed for either a fixed length of time (20 min) or until there was no further CO 2 measured in the effluent gas. Results from the ethylene aromatization reactions were shown to serve as an excellent surrogate for CFP reactivity and indicated that the use of model compound studies can effectively be used to understand reaction and regeneration processes from biomass CFP. Both sets of results indicate that a spent ZSM-5 used for biomass CFP could be fully regenerated at 650 degrees C and 700 °C within 20 min, whereas regeneration temperatures of 550 °C and 600 °C required longer regeneration temperatures and in the case of regeneration at 500 °C, there may be coke species that are not removed and the catalyst activity may never be fully restored. Characterization by pyridine diffuse reflectance infrared spectroscopy, thermogravimetric analysis coupled with infrared spectroscopy, and N 2 physisorption showed that higher regeneration temperatures are more effective for restoring Bronsted acid sites and catalyst mesoporosity by rapidly removing aromatic coke deposits. In conclusion, regeneration at 650 °C and 700 °C led to a slightly higher total porosity as compared to the pristine catalyst, which was attributed to the formation of additional mesoporosity from catalyst steaming.

09 BIOMASS FUELS↗