Advanced thermally stable jet fuels. Technical progress report, 1995

The Penn State program in advanced thermally stable jet fuels has five components:(1) development of mechanisms of degradation and solids formation; (2) quantitative measurement of growth of sub- micrometer and micrometer sized particles suspended in fuels during thermal stressing; (3) characterization of carbonaceous deposits by various instrumental and microscopic methods; (4) elucidation of the role of additives in retarding the formation of carbonaceous solids; and (5) assessment of the potential of producing high yields of cycloalkanes and hydroaromatics by direct liquefaction of coal. Progress reports for these tasks are presented

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, April--June 1995

Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting polycyclic aromatic units and the reactions of various oxygen functional groups. Here in this quarterly, we report on our continued effort on hydrodeoxygenation of O-containing polycyclic model compounds using novel organometallic catalyst precursors. Compounds containing oxygen functional groups, especially phenols, are undesirable components of coal-derived liquids. Removal of these compounds from the products of coal liquefaction is required. A beneficial alternative would be the removal of these compounds, or the prevention of their formation, during the liquefaction reaction itself, rather than as a separate processing step. A novel organometallic catalyst precursor containing Co and Mo has been studied as a potential hydrogenation catalyst for coal liquefaction. To ascertain the hydrodeoxygenation activity of this catalyst under liquefaction conditions, model compounds were investigated. Anthrone, 2,6-di-t-butyl-4-methyl-phenol, dinaphthyl ether, and xanthene were reacted in the presence of the Co-Mo catalyst precursor and a precursor containing only Mo over a range of temperatures, providing a comparison of conversions to deoxygenated products. These conversions give an indication of the hydrodeoxygenating abilities of organometallic catalyst precursors within a coal liquefaction system. For example, at 400{degrees}C dinaphthylether was converted 100% (4.5% O-containing products) in the presence of the Co-Mo organometallic precursor, compared to 76.5% conversion (7.4% O-products) in the presence of the Mo catalyst

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, April--June 1996

This quarterly report describes our recent work on two related subjects: effect of using organometallic catalyst precursor on hydrodeoxygenation under coal liquefaction conditions, and the effect of mineral matters in liquefaction reactions of coals. Oxygen functionalities, especially phenols, are undesirable components of coal derived liquids. Removal of these compounds from the products of coal liquefaction is required. A beneficial alternative would be the removal of these functionalities, or the prevention of their formation, during the liquefaction process. Organometallic precursors of Co, Ni and Mo have been studied as catalysts. To ascertain the hydrodeoxygenation properties of these catalysts under liquefaction conditions, model compounds were investigated. Anthrone, Dibutylmethyl phenol, dinaphthyl ether and xanthene were studied to provide a comparison of conversions to deoxygenated products. Studies of the deoxygenating abilities of these catalyst precursors in coal liquefaction systems have also been performed. Improvements in conversion and product quality are observed. Both these factors are dependent on the coal used. It is also considered that some mineral matters in coal may have catalytic actions. Demineralization by successive HCl/HF treatments of a low rank coal has demonstrated that removal of the inherent mineral matter imparts no serious detrimental effect upon low temperature liquefaction. It appears that elimination of such species allows for better access for gaseous H{sub 2}, as suggested by previous studies

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, October 1995--December 1995

Coal liquefaction involves cleavage of methylene, dimethylene and ether bridges connecting polycyclic aromatic units and the reactions of various oxygen functional groups. Here in this quarterly, we report on the catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds in the reactions of dibenzothiophene (DBT) with hydrogen under conditions related to coal liquefaction. The catalytic effects of several molybdenum-, cobalt-, and iron-containing compounds have been examined in the hydrogenation and hydrodesulfurization reactions of dibenzothiophene (DBT) under conditions related to coal liquefaction. The metal compounds are candidate catalyst precursors for direct coal liquefaction. The reactions were carried out in batch microautoclave reactors at 400{degrees}C for 30 minutes with 6.9 MPa (cold) hydrogen pressure, and tridecane solvent. A metal loading of 0.5 mol% resulted in low conversion and only hydrogenation. Addition of sulfur in 4:1 molar ratio led only to a minor increase in conversion and hydrodesulfurization. The use of a higher boiling solvent (octadecane vs. tridecane) was beneficial in providing increased conversion, hydrodesulfurization, and hydrogenation. An increase in metal compound loading to 36.2 mol% led to a dramatic increase in conversion, hydrodesulfurization, and hydrocracking. Molybdenum hexacarbonyl at 36 mol% loading, with added sulfur at 6:1 ratio and octadecane solvent, gave 100% conversion of dibenzothiophene to other products with 100% hydrodesulfurization. Ammonium tetrathiomolybdate and molybdenum(III) chloride are less active under similar conditions. A cobalt-molybdenum thiocubane complex gave unexpectedly low conversions. Iron and cobalt carbonyls also provided very low conversions, even with added sulfur

Competition of crystal field splitting and Hund's rule coupling in two-orbital magnetic metal-insulator transitions

Competition of crystal field splitting and Hund's rule coupling in magnetic metal-insulator transitions of half-filled two-orbital Hubbard model is investigated by multi-orbital slave-boson mean field theory. We show that with the increase of Coulomb correlation, the system firstly transits from a paramagnetic (PM) metal to a {\it N\'{e}el} antiferromagnetic (AFM) Mott insulator, or a nonmagnetic orbital insulator, depending on the competition of crystal field splitting and the Hund's rule coupling. The different AFM Mott insulator, PM metal and orbital insulating phase are none, partially and fully orbital polarized, respectively. For a small $J_{H}$ and a finite crystal field, the orbital insulator is robust. Although the system is nonmagnetic, the phase boundary of the orbital insulator transition obviously shifts to the small $U$ regime after the magnetic correlations is taken into account. These results demonstrate that large crystal field splitting favors the formation of the orbital insulating phase, while large Hund's rule coupling tends to destroy it, driving the low-spin to high-spin transition.Comment: 4 pages, 4 figure

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Technical progress report, July--September 1996

This quarterly report describes recent work on two related subjects: (1) effect of dispersed molybdenum catalyst precursor and the influence of water addition on C-O bond cleavage, aromatic hydrogenation and hydrodeoxygenation under coal liquefaction conditions, and (2) the effect of dispersed molybdenum catalyst precursor on the molecular weight reduction and desulfurization of petroleum resids related to coal/petroleum resids coprocessing. Technical progress on the C-O bond cleavage of 2,2{prime}-dinaphthyl ether and high temperature simulated distillation GC and HDS study on catalytic upgrading of atmospheric and vacuum resids

Sparsity without the Complexity: Loss Localisation using Tree Measurements

We study network loss tomography based on observing average loss rates over a set of paths forming a tree -- a severely underdetermined linear problem for the unknown link loss probabilities. We examine in detail the role of sparsity as a regularising principle, pointing out that the problem is technically distinct from others in the compressed sensing literature. While sparsity has been applied in the context of tomography, key questions regarding uniqueness and recovery remain unanswered. Our work exploits the tree structure of path measurements to derive sufficient conditions for sparse solutions to be unique and the condition that $\ell_1$ minimization recovers the true underlying solution. We present a fast single-pass linear algorithm for $\ell_1$ minimization and prove that a minimum $\ell_1$ solution is both unique and sparsest for tree topologies. By considering the placement of lossy links within trees, we show that sparse solutions remain unique more often than is commonly supposed. We prove similar results for a noisy version of the problem

Advanced thermally stable jet fuels: Technical progress report, October 1994--December 1994

There are five tasks within this project on thermally stable coal-based jet fuels. Progress on each of the tasks is described. Task 1, Investigation of the quantitative degradation chemistry of fuels, has 5 subtasks which are described: Literature review on thermal stability of jet fuels; Pyrolytic and catalytic reactions of potential endothermic fuels: cis- and trans-decalin; Use of site specific {sup 13}C-labeling to examine the thermal stressing of 1-phenylhexane: A case study for the determination of reaction kinetics in complex fuel mixtures versus model compound studies; Estimation of critical temperatures of jet fuels; and Surface effects on deposit formation in a flow reactor system. Under Task 2, Investigation of incipient deposition, the subtask reported is Uncertainty analysis on growth and deposition of particles during heating of coal-derived aviation gas turbine fuels; under Task 3, Characterization of solid gums, sediments, and carbonaceous deposits, is subtask, Studies of surface chemistry of PX-21 activated carbon during thermal degradation of jet A-1 fuel and n-dodecane; under Task 4, Coal-based fuel stabilization studies, is subtask, Exploratory screening and development potential of jet fuel thermal stabilizers over 400 C; and under Task 5, Exploratory studies on the direct conversion of coal to high quality jet fuels, are 4 subtasks: Novel approaches to low-severity coal liquefaction and coal/resid co-processing using water and dispersed catalysts; Shape-selective naphthalene hydrogenation for production of thermally stable jet fuels; Design of a batch mode and a continuous mode three-phase reactor system for the liquefaction of coal and upgrading of coal liquids; and Exploratory studies on coal liquids upgrading using mesopores molecular sieve catalysts. 136 refs., 69 figs., 24 tabs

Advanced thermally stable jet fuels: Technical progress report, July 1994--September 1994

There are five tasks within this project on thermally stable coal-based jet fuels. Progress on each of the tasks is described. Task 1, Investigation of the quantitative degradation chemistry of fuels, has 3 subtasks which are described: Pyrolysis of n-alkylbenzenes; Thermal decomposition of n-tetradecane in near-critical region; and Re-examining the effects of reactant and inert gas pressure on tetradecane pyrolysis--Effect of cold volume in batch reactor. Under Task 2, Investigation of incipient deposition, the subtask reported is Uncertainty analysis on growth and deposition of particles during heating of coal-derived aviation gas turbine fuels; under Task 3, Investigation of the quantitative degradation chemistry of fuels, is subtask, Effects of high surface area activated carbon and decalin on thermal degradation of jet A-1 fuel and n-dodecane; under Task 4, Coal-based fuel stabilization studies, is subtask, Screening potential jet fuel stabilizers using the model compound dodecane; and under Task 5, Exploratory studies on the direct conversion of coal to high quality jet fuels, is subtask, Shape-selective naphthalene hydrogenation for production of thermally stable jet fuels. 25 refs., 64 figs., 22 tabs