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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↗

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↗

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↗

Simulation of the supercritical CO 2 recompression Brayton power cycle with a high-temperature regenerator

The supercritical carbon dioxide (sCO 2 ) recompression Brayton cycle promises higher efficiency and lower capital cost than traditional steam Rankine power cycles. However, achieving high efficiency requires large, highly effective recuperators. Regenerators may be a low-cost alternative to printed circuit and micro-tube heat exchangers for recuperation in sCO 2 power cycles. Regenerators are a periodic heat exchanger in which thermal energy is extracted from the hot stream, stored in solid media, and then released to the cold stream at a later time. Fixed bed regenerators with valves to direct fluid are the preferred method for implementing regenerators in power cycles, but the inherently transient nature of these systems has not been characterized for this application. This study presents the simulation of a high-temperature regenerator within a 10 MWe sCO 2 recompression Brayton cycle. A transient, one-dimensional regenerator model presented in a previous study is used to simulate the regenerator. Dynamic heat exchanger models are also developed for the precooler, low-temperature recuperator, and primary heat exchanger, and the compressors and the turbine are modeled with off-design performance maps. We assess two regenerator-valve design options; one for fast switching, and one for reduced flow rate fluctuations. System simulation finds that both designs see significant fluctuations in turbomachinery flow rate, turbomachinery and system power, and regenerator discharge process outlet temperature. While designing the regenerator-valve subsystem for lower fluctuations is possible, the regenerator cold discharge temperature and net power still fluctuate by ±77.6°C and 6%, respectively. Increasing buffer volume is not effective at sufficiently reducing these fluctuations, but adding a packed bed in between the regenerator and the primary heat exchanger can reduce regenerator discharge process outlet temperature fluctuations to 6.4°C. Further reductions could be possible by increasing the size of this packed bed.

42 ENGINEERING↗

Liver-specific deletion of LASS2 delayed regeneration of mouse liver after partial hepatectomy

The capacity of liver regeneration is critical for patients with liver diseases. However, cellular and molecular mechanisms of liver regeneration are still incompletely defined. Here, we assessed roles of LASS2 in liver regeneration following partial hepatectomy (PHx) in mice. Our results showed that protein level of LASS2 remarkably increased during liver regeneration after PHx in wildtype (WT) mice. Comparing to WT mice, liver regeneration index after PHx was significantly decreased from day 1 to day 5 in liver-specific LASS2 knockout (LASS2-LKO) mice. Interestingly, liver mass of LASS2-LKO mice could sufficiently recover at day 14 after PHx. Immunohistochemistry (IHC) and western blot analyses revealed that proliferation markers, such as PCNA and Ki67, were potently reduced during liver regeneration in LASS2-LKO mice. In addition, several cell cycle related molecules, such as cyclin A, CDK2 and p-Rb, were decreased in LASS2-LKO mice after PHx. Co-immunoprecipitation assay further revealed a decreased formation of CDK4/cyclin D1 complex after PHx in LASS2-LKO mice. However, phosphorylation of Akt was significantly activated from day 2 after PHx in LASS2-LKO mice when compared with that in WT mice, which may explain the recovery of liver mass at the late stage of liver regeneration in LASS2-LKO mice. Taken together, we conclude that LASS2 plays an important role in efficient liver regeneration in response to PHx. - Highlights: • LASS2 remarkably increased during liver regeneration after PHx. • Liver regeneration is delayed by LASS2 knockout in mice. • Proliferation and cell cycle entry of hepatocytes after PHx is impaired by LASS2 knockout in mice. • Knockout of LASS2 activated Akt signaling and increased cell size of hepatocytes during liver regeneration.

60 APPLIED LIFE SCIENCES↗

Regeneration of anion-exchange resins for cyclic selenium removal from industrial wastewaters

Application of ion exchange for the removal of selenium (Se) oxyanions from industrial wastewaters is often limited by ineffective regeneration of the ion-exchange resins, particularly in complex systems containing competing ions, such as coal-ash leachate containing high-sulfate concentrations and heavy metal ions. Here, in this study, it was first demonstrated that while conventional regeneration with sodium chloride (NaCl) is effective for simulated wastewater, with ∼80% efficiency, NaCl fails to regenerate resin loaded with real industrial wastewater, achieving less than 20% efficiency. To overcome this challenge, a two-step regeneration process was investigated using a sodium carbonate (Na 2 CO 3 ) solution for elution, followed by a NaCl solution for restoration. Compared to the one-step NaCl regeneration, this integrated process restored more than 80% of the resin's capacity with real industrial wastewaters. Beyond demonstrating regeneration performance, this research emphasizes fundamental mechanistic interpretations of the observed regeneration behavior across different water matrices and experimental conditions. Particularly, accounting for pH-dependent carbonate speciation, it is proposed that the elution step exploits the resin's strong affinity for divalent carbonate ions to displace strongly bound contaminants, while the subsequent restoration step relies mainly on the mass action effects of chloride ions to regenerate the resin sites. The protocol was optimized to achieve rapid regeneration (<10 min) using moderate chemical concentrations (0.5 M) in treating real leachate. In batch cyclic experiments, Se regeneration reached nearly complete recovery after five consecutive sorption and desorption cycles, while in the fixed-bed system, the regeneration efficiency remained at approximately 80% after five cycles.

Anion-exchange resin↗

Cost comparison of printed circuit heat exchanger to low cost periodic flow regenerator for use as recuperator in a s-CO 2 Brayton cycle

Supercritical Carbon Dioxide (sCO 2 ) power cycles have the potential to deliver high efficiency at low cost. However, in order for an sCO 2 cycle to reach high efficiency, highly effective recuperators are needed. These recuperative heat exchangers must transfer heat at a rate that is substantially larger than the heat transfer to the cycle itself and can therefore represent a significant portion of the power block costs. Regenerators are proposed as a cost saving alternative to high cost printed circuit recuperators for this application. A regenerator is an indirect heat exchanger which periodically stores and releases heat to the working fluid. The simple design of a regenerator can be made more inexpensively compared to current options. The objective of this paper is a detailed evaluation of regenerators as a competing technology for recuperators within an sCO 2 Brayton cycle. The level of the analysis presented here is sufficient to identify issues with the regenerator system in order to direct future work and also to clarify the potential advantage of pursuing this technology. A reduced order model of a regenerator is implemented into a cycle model of an sCO 2 Brayton cycle. An economic analysis investigates the cost savings that is possible by switching from recuperative heat exchangers to switched-bed regenerators. The cost of the regenerators was estimated using the amount of material required if the pressure vessel is sized using ASME Boiler Pressure Vessel Code (BPVC) requirements. The cost of the associated valves is found to be substantial for the regenerator system and is estimated in collaboration with an industrial valve supplier. The result of this analysis suggests that a 21.2% reduction in the contribution to the Levelized Cost of Electricity (LCoE) from the power block can be realized by switching to a regenerator-based system.

24 POWER TRANSMISSION AND DISTRIBUTION↗