Durability testing at 5 atmospheres of advanced catalysts and catalyst supports for gas turbine engine combustors

The durability of CATCOM catalysts and catalyst supports was experimentally demonstrated in a combustion environment under simulated gas turbine engine combustor operating conditions. A test of 1000 hours duration was completed with one catalyst using no. 2 diesel fuel and operating at catalytically-supported thermal combustion conditions. The performance of the catalyst was determined by monitoring emissions throughout the test, and by examining the physical condition of the catalyst core at the conclusion of the test. Tests were performed periodically to determine changes in catalytic activity of the catalyst core. Detailed parametric studies were also run at the beginning and end of the durability test, using no. 2 fuel oil. Initial and final emissions for the 1000 hours test respectively were: unburned hydrocarbons (C3 vppm):0, 146, carbon monoxide (vppm):30, 2420; nitrogen oxides (vppm):5.7, 5.6

Durability testing at one atmosphere of advanced catalysts and catalyst supports for automotive gas turbine engine combustors, part 1

The durability of catalysts and catalyst supports in a combustion environment was experimentally demonstrated. A test of 1000 hours duration was completed with two catalysts, using diesel fuel and operating at catalytically supported thermal combustion conditions. The performance of the catalysts was determined by monitoring emissions throughout the test, and by examining the physical condition of the catalyst core at the conclusion of the test. The test catalysts proved to be capable of low emissions operation after 1000 hours diesel aging, with no apparent physical degradation of the catalyst support

High Temperature, High Pressure Oxidation of Primary Sludges

The problem of disposal of high ash papermill sludges has yet to be resolved. High temperature, high pressure wet air oxidation may have the potential to fill this gap in our technology. A sample of high ash primary sludge was obtained, thickened, wet air oxidized, purified, and evaluated for brightness and abrasiveness. The product was grossly discolored with iron oxide. However, removal of the oxide yielded a high brightness product with low abrasiveness. This product appeared to be well suited for use as a filler material. In order for this process to be acceptable as a method for obtaining a reusable product from high ash papermill sludge, it will be necessary to keep the iron oxide out of the product

Synthesis of cocrystallized USY/ZSM-5 zeolites from kaolin and its use as fluid catalytic cracking catalysts

[EN] A series of samples of cocrystallized USY/ZSM-5 zeolites were synthesized from kaolin and silica following a sequential two-step procedure with varying content of ZSM-5 (5-25 wt%). The presence of the ZSM-5 phases was confirmed by XRD and Si-29-NMR. The samples were stabilized by steaming and tested as FCC catalysts in the cracking of vacuum gasoil. The results obtained show that effectiveness of ZSM-5 as a propylene booster is enhanced when zeolites USY and ZSM-5 were synthesized in the same kaolin material, instead of using merely the physical mixtures of the two zeolites. This enhancement is attributed to the higher ability of ZSM-5 to crack larger olefins and suppress hydrogen-transfer to the gasoline fraction when the zeolites are grown together.This work has been supported by the Spanish Government MINECO through "Severo Ochoa" SEV-2016-0683, CTQ2015-67592-P and CTQ2015-68951-C3-1-R, by the European Union through ERC-AdG-2014-671093 (SynCatMatch) and by the Fundacion Ramon Areces through a research contract of the "Life and Materials Science" program. The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization.Ghrib, Y.; Frini-Srasra, N.; Srasra, E.; Martínez-Triguero, J.; Corma Canós, A. (2018). Synthesis of cocrystallized USY/ZSM-5 zeolites from kaolin and its use as fluid catalytic cracking catalysts. Catalysis Science & Technology. 8(3):716-725. https://doi.org/10.1039/c7cy01477eS71672583Corma, A., & Wojciechowski, B. W. (1985). The Chemistry of Catalytic Cracking. Catalysis Reviews, 27(1), 29-150. doi:10.1080/01614948509342358Martínez, C., & Corma, A. (2011). Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes. Coordination Chemistry Reviews, 255(13-14), 1558-1580. doi:10.1016/j.ccr.2011.03.014O’Connor, P. (2007). Chapter 15 Catalytic cracking: The Future of an Evolving Process. Studies in Surface Science and Catalysis, 227-251. doi:10.1016/s0167-2991(07)80198-4Biswas, J., & Maxwell, I. E. (1990). Recent process- and catalyst-related developments in fluid catalytic cracking. Applied Catalysis, 63(1), 197-258. doi:10.1016/s0166-9834(00)81716-9CORMA, A., HUBER, G., SAUVANAUD, L., & OCONNOR, P. (2007). Processing biomass-derived oxygenates in the oil refinery: Catalytic cracking (FCC) reaction pathways and role of catalyst. Journal of Catalysis, 247(2), 307-327. doi:10.1016/j.jcat.2007.01.023Corma, A., & Sauvanaud, L. (2013). FCC testing at bench scale: New units, new processes, new feeds. Catalysis Today, 218-219, 107-114. doi:10.1016/j.cattod.2013.03.038Buchanan, J. . (2000). The chemistry of olefins production by ZSM-5 addition to catalytic cracking units. Catalysis Today, 55(3), 207-212. doi:10.1016/s0920-5861(99)00248-5Adewuyi, Y. G., Klocke, D. J., & Buchanan, J. S. (1995). Effects of high-level additions of ZSM-5 to a fluid catalytic cracking (FCC) RE-USY catalyst. Applied Catalysis A: General, 131(1), 121-133. doi:10.1016/0926-860x(95)00124-7Woltermann, G. M., Magee, J. S., & Griffith, S. D. (1993). Chapter 4 Commercial Preparation and Characterization of FCC Catalysts. Fluid Catalytic Cracking: Science and Technology, 105-144. doi:10.1016/s0167-2991(08)63827-6Xu, M., Cheng, M., & Bao, X. (2000). Growth of ultrafine zeolite Y crystals on metakaolin microspheres. Chemical Communications, (19), 1873-1874. doi:10.1039/b005787hLi, T., Liu, H., Fan, Y., Yuan, P., Shi, G., Bi, X. T., & Bao, X. (2012). Synthesis of zeolite Y from natural aluminosilicate minerals for fluid catalytic cracking application. Green Chemistry, 14(12), 3255. doi:10.1039/c2gc36101aWei, B., Liu, H., Li, T., Cao, L., Fan, Y., & Bao, X. (2010). Natural rectorite mineral: A promising substitute of kaolin for in-situ synthesis of fluid catalytic cracking catalysts. AIChE Journal, 56(11), 2913-2922. doi:10.1002/aic.12195Ding, J., Liu, H., Yuan, P., Shi, G., & Bao, X. (2013). Catalytic Properties of a Hierarchical Zeolite Synthesized from a Natural Aluminosilicate Mineral without the Use of a Secondary Mesoscale Template. ChemCatChem, 5(8), 2258-2269. doi:10.1002/cctc.201300049Yue, Y., Liu, H., Yuan, P., Li, T., Yu, C., Bi, H., & Bao, X. (2014). From natural aluminosilicate minerals to hierarchical ZSM-5 zeolites: A nanoscale depolymerization–reorganization approach. Journal of Catalysis, 319, 200-210. doi:10.1016/j.jcat.2014.08.009Holmes, S. M., Khoo, S. H., & Kovo, A. S. (2011). The direct conversion of impure natural kaolin into pure zeolite catalysts. Green Chemistry, 13(5), 1152. doi:10.1039/c1gc15099eMintova, S., Valtchev, V., Vultcheva, E., & Veleva, S. (1992). Crystallization kinetics of zeolite ZSM-5. Zeolites, 12(2), 210-215. doi:10.1016/0144-2449(92)90086-5P. H. Schipper , F. G.Dwyer , P. T.Sparrell , S.Mizrahi and J. A.Herbst , in Fluid Catalytic Cracking , American Chemical Society , 1988 , ch. 5, vol. 375 , pp. 64–86Degnan, T. F., Chitnis, G. K., & Schipper, P. H. (2000). History of ZSM-5 fluid catalytic cracking additive development at Mobil. Microporous and Mesoporous Materials, 35-36, 245-252. doi:10.1016/s1387-1811(99)00225-5Corma, A., & Martínez-Triguero, J. (1994). Kinetics of gasoil cracking and catalyst decay on SAPO-37 and USY molecular sieves. Applied Catalysis A: General, 118(2), 153-162. doi:10.1016/0926-860x(94)80310-2Corma, A., Martı́nez-Triguero, J., & Martı́nez, C. (2001). The Use of ITQ-7 as a FCC Zeolitic Additive. Journal of Catalysis, 197(1), 151-159. doi:10.1006/jcat.2000.3065Goodyear, J., & Duffin, W. J. (1961). An X-ray examination of an exceptionally well crystallized kaolinite. Mineralogical Magazine and Journal of the Mineralogical Society, 32(254), 902-907. doi:10.1180/minmag.1961.032.254.05Salter, T. L., & Riley, W. E. (1994). Quartz determination in kaolin at the 0.1% level. Analytica Chimica Acta, 286(1), 49-55. doi:10.1016/0003-2670(94)80175-4JOHNSON, M. (1978). Estimation of the zeolite content of a catalyst from nitrogen adsorption isotherms. Journal of Catalysis, 52(3), 425-431. doi:10.1016/0021-9517(78)90346-9Peters, A. W. (1993). Chapter 6 Instrumental Methods of FCC Catalyst Characterization. Fluid Catalytic Cracking: Science and Technology, 183-221. doi:10.1016/s0167-2991(08)63829-xBLASCO, T., CORMA, A., & MARTINEZTRIGUERO, J. (2006). Hydrothermal stabilization of ZSM-5 catalytic-cracking additives by phosphorus addition. Journal of Catalysis, 237(2), 267-277. doi:10.1016/j.jcat.2005.11.011Corma, A., Fornes, V., Kolodziejski, W., & Martineztriguero, L. J. (1994). Orthophosphoric Acid Interactions with Ultrastable Zeolite-Y: Infrared and NMR Studies. Journal of Catalysis, 145(1), 27-36. doi:10.1006/jcat.1994.1004Klinowski, J. (1991). Solid-state NMR studies of molecular sieve catalysts. Chemical Reviews, 91(7), 1459-1479. doi:10.1021/cr00007a010Engelhardt, G., Lohse, U., Samoson, A., Mägi, M., Tarmak, M., & Lippmaa, E. (1982). High resolution 29Si n.m.r. of dealuminated and ultrastable Y-zeolites. Zeolites, 2(1), 59-62. doi:10.1016/s0144-2449(82)80042-0Biswas, J., & Maxwell, I. E. (1990). Octane enhancement in fluid catalytic cracking. Applied Catalysis, 58(1), 1-18. doi:10.1016/s0166-9834(00)82274-5WIELERS, A. (1991). Relation between properties and performance of zeolites in paraffin cracking. Journal of Catalysis, 127(1), 51-66. doi:10.1016/0021-9517(91)90208-lHaas, A., Finger, K.-E., & Alkemade, U. (1994). Application of the energy gradient selectivity concept to fluid catalytic cracking catalysts. Applied Catalysis A: General, 115(1), 103-120. doi:10.1016/0926-860x(94)80381-

Memorandum and related articles regarding Inadequate Representation and Unfunded Pension Liabilities, 1979

Memo to all consultants and attorneys, with an attached distribution list including articles: On trial: A union’s fairness”. Business Week, 13 August, 1979. “Unfunded Pension Liabilities: A Rein On Their Growth- For Now”. Business Week, 13 August, 1979

Development of a platinum-thorium oxide alloy for resistojet thruster use

Platinum-thorium oxide alloy for resistojet thruster showing increase in stress rupture lif

Critical research and advanced technology (CRT) support project

A critical technology base for utility and industrial gas turbines by planning the use of coal-derived fuels was studied. Development tasks were included in the following areas: (1) Combustion - investigate the combustion of coal-derived fuels and methods to minimize the conversion of fuel-bound nitrogen to NOx; (2) materials - understand and minimize hot corrosion; (3) system studies - integrate and focus the technological efforts. A literature survey of coal-derived fuels was completed and a NOx emissions model was developed. Flametube tests of a two-stage (rich-lean) combustor defined optimum equivalence ratios for minimizing NOx emissions. Sector combustor tests demonstrated variable air control to optimize equivalence ratios over a wide load range and steam cooling of the primary zone liner. The catalytic combustion of coal-derived fuels was demonstrated. The combustion of coal-derived gases is very promising. A hot-corrosion life prediction model was formulated and verified with laboratory testing of doped fuels. Fuel additives to control sulfur corrosion were studied. The intermittent application of barium proved effective. Advanced thermal barrier coatings were developed and tested. Coating failure modes were identified and new material formulations and fabrication parameters were specified. System studies in support of the thermal barrier coating development were accomplished

Catalytic combustion of actual low and medium heating value gases

Catalytic combustion of both low and medium heating value gases using actual coal derived gases obtained from operating gasifiers was demonstrated. A fixed bed gasifier with a complete product gas cleanup system was operated in an air blown mode to produce low heating value gas. A fluidized bed gasifier with a water quench product gas cleanup system was operated in both an air enriched and an oxygen blown mode to produce low and medium, heating value gas. Noble metal catalytic reactors were evaluated in 12 cm flow diameter test rigs on both low and medium heating value gases. Combustion efficiencies greater than 99.5% were obtained with all coal derived gaseous fuels. The NOx emissions ranged from 0.2 to 4 g NO2 kg fuel

Compatibility of grain-stabilized platinum with candidate propellants for resistojets

Resistojets are candidates for space station auxiliary propulsion, and should be characterized by both long life and multipropellant operations, requirements limited by available materials. Grain stabilized platinum is examined for use as a resistojet thruster material. Use of platinum in other applications indicates it can be used at moderately high temperatures for extended periods of time. Past results indicate that grain-stabilized platinum should be sufficiently inert in candidate propellant environments. Therefore, compatibility of platinum-yttria (P/Y2O3) and platinum-zirconia (Pt/ZrO2) with carbon dioxide, methane, hydrogen and ammonia is examined. A series of 1000 hr tests in CO2, H2, and NH3 is conducted at 1400 C and a series of 1000 hr tests in CH4 is conducted at about 500 C. Scanning electron microscopy, Auger electron spectroscopy and depth profiling analysis are then used to determine the effects of propellants on the material surface, to evaluate possible material contamination and to evaluate grain growth. The results indicate that there is carbon deposition on the surface of the Pt/Y2O3 and Pt/ZrO2 in both the CO2 and CH4 environments. In the H2 environment, the Pt/Y2O3 and Pt/ZrO2 specimen surfaces are roughened. After exposure to the NH3 environment, the Pt/Y2O3 and Pt/ZrO2 are roughened and pitted over the entire heated area with some pitted areas along the grain boundaries. SEM photos show grain growth in cross-sectional views of all the Pt/Y2O3 samples and the Pt/ZrO2 samples, except that tested in methane. Mass loss measurements indicate that Pt/Y2O3 and Pt/ZrO2 would last in excess of 200,000 hr in each propellant environment. However, in NH3 both Pt/Y2O3 and Pt/ZrO2 are severely pitted, with voids up to 50 percent into the material. Pt/Y2O3 and Pt/ZrO2 are not recommended for high temperature service in NH3