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651 records · Page 37

Relating FTS Catalyst Properties to Performance

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.

Zirconia↗

NASA's Space Launch System Begins Integration, Stacking in Preparation for Artemis I Launch

The Artemis era of human lunar exploration is nearing take-off as NASA’s new super heavy-lift launch vehicle, the Space Launch System (SLS), begins stack-ing and integration operations in mid-2020 at Kennedy Space Center (KSC) in Florida. With a planned upgrade path to progressively more powerful vehicles and availability in crew and cargo configurations, SLS provides a unique and flexible launch solution to send crew, large-scale infrastructure and robotic probes to deep space. The SLS Block 1 vehicle, the initial variant to fly, is optimized for lunar missions with a proven propulsion system consisting of four liquid hydrogen (LH2)/liquid oxygen (LOX)-fed RS-25 engines and twin five-segment solid rocket boosters (SRBs). The Block 1 vehicle can also be outfitted with an industry-standard 5 m-class payload fairing (the “cargo” configuration) and will launch at least 27 metric tons (t) of mass to trans-lunar injection (TLI). SLS is the backbone of NASA’s Artemis program, which will return the agency’s human spaceflight program to the Moon for the first time since 1972. For the Artemis I mission, SLS will send an uncrewed Orion spacecraft to TLI, where it will enter a distant retrograde lunar orbit and fly 38,000 nmi past the Moon – farther than any spacecraft built for humans has ever traveled. The SLS Block 1 vehicle for Artemis I completed manufacturing in 2019. Several elements, including the upper stage, have been delivered to the Exploration Ground Systems (EGS) program at KSC and are being prepped for integration and stack-ing. The five-segment solid rocket boosters – the largest and most powerful ever built for flight – are also complete. The booster motor segments for the Artemis I flight are scheduled to ship from prime contractor Northrop Grumman’s Utah facilities and begin stacking and integration at KSC in June 2020. The SLS core stage is the largest rocket stage NASA has ever built in terms of volume and height, and includes the avionics and the tanks that feed cryogenic propellant to the four RS-25s (formerly Space Shuttle Main Engines [SSMEs]). They have been modified with an updated controller and nozzle insulation to protect them from the hotter launch environment. The SLS core stage is currently being test-ed at NASA’s Stennis Space Center (SSC) in a series of “green run” tests to verify it meets design and performance requirements. Following the green run test series, which is scheduled to culminate with a full-duration hot-fire of the four RS-25 engines, the core stage will ship to KSC and be stacked between the sol-id rocket boosters in the Vehicle Assembly Building (VAB). Integration of the vehicle will continue with the upper stage, known as the Interim Cryogenic Propulsion Stage (ICPS) and the Launch Vehicle Stage Adapter (LVSA) on the core stage. Another adapter, the Orion Stage Adapter (OSA), connects SLS to Orion and provides housing for 13 6U CubeSat payloads manifested on Artemis I. The CubeSats will be released in deep space after Orion separates from the vehicle, and the flight marks the first ride share opportunity for independent small-sats to deep space. The second major SLS variant to come online, Block 1B, replaces the single-engine ICPS with a four-engine LH2/LOX Exploration Upper Stage (EUS). This more powerful upper stage, along with other vehicle up-grades, will enable the Block 1B vehicle to launch 38-42 t to TLI, depending on crew or cargo configuration. The final evolution of the vehicle, Block 2, will onramp evolved solid rocket boosters to increase mass to TLI to 43-46 t, de-pending on crew or cargo configuration. The Block 1B/Block 2 vehicles can be outfitted with an 8.4 m-diameter payload fairing in 19.1 m or 27.4 m lengths, to provide unprecedented volume for payloads. With the initial Block 1 vehicle completely manufactured and the core stage in final testing before shipping to KSC, the SLS Program and its industry partners have made significant progress manufacturing subsequent vehicles. For the second Block 1 vehicle, the solid rocket motor segments are complete, as are the RS-25 engines with controllers. All five major components of the Artemis II core stage – the forward skirt, LOX and LH2 tanks, intertank and engine section – are manufactured and technicians are installing subsystems at NASA’s rocket factory, Michoud Assembly Facility. The RL-10 engine for the Artemis II ICPS is complete and panels have been machined for its LH2 tank. In addition, panels are machined for the vehicle’s two adapters, with welding scheduled to begin in summer 2020. Flight hard-ware is also in production for the third SLS vehicle, with several booster motor segments cast. The pace of development on the EUS has increased, with the goal to complete Critical Design Review (CDR) in December 2020. Several EUS test rings have been machined at Michoud. The EUS is designed to exe-cute a variety of missions – human spaceflight, deployment of deep-space infra-structure, or high-C3 missions to the outer solar system – with crew and cargo configurations available beginning in the mid-2020s. The near-term goal for the nation’s powerful new space exploration asset, however, is to launch the Arte-mis program, and send the first woman and the next man to the lunar surface. At the Astrodynamics Specialist Conference, the SLS program will update the community on the progress of the initial Block 1 vehicle in final green run test-ing, integration and stacking. In addition, this paper will provide an update to the community on the manufacturing status of subsequent Block 1 and Block 1B vehicles.

Steve Creech↗

Influence of the size and protonation state of acidic residue 85 on the absorption spectrum and photoreaction of the bacteriorhodopsin chromophore

The consequences of replacing Asp-85 with glutamate in bacteriorhodopsin, as expressed in Halobacterium sp. GRB, were investigated. Similarly to the in vitro mutated and in Escherichia coli expressed protein, the chromophore was found to exist as a mixture of blue (absorption maximum 615 nm) and red (532 nm) forms, depending on the pH. However, we found two widely separated pKa values (about 5.4 and 10.4 without added salt), arguing for two blue and two red forms in separate equilibria. Both blue and red forms of the protein are in the two-dimensional crystalline state. A single pKa, such as in the E. coli expressed protein, was observed only after solubilization with detergent. The photocycle of the blue forms was determined at pH 4.0 with 610 nm photoexcitation, and that of the red forms at pH 10.5 and with 520 nm photoexcitation, in the time-range of 100 ns to 1 s. The blue forms produced no M, but a K- and an L-like intermediate, whose spectra and kinetics resembled those of blue wild-type bacteriorhodopsin below pH 3. The red forms produced a K-like intermediate, as well as M and N. Only the red forms transported protons. Specific perturbation of the neighborhood of the Schiff base by the replacement of Asp-85 with glutamate was suggested by (1) the shift and splitting of the pKa for what is presumably the protonation of residue 85, (2) a 36 nm blue-shift in the absorption of the all-trans red chromophore and a 25 nm red-shift of the 13-cis N chromophore, as compared to wild-type bacteriorhodopsin and its N intermediate, and (3) significant acceleration of the deprotonation of the Schiff base at pH 7, but not of its reprotonation and the following steps in the photocycle.

Non-NASA Center↗