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. 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

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

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

Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction. Technical progress report, July--September 1993

In this quarter, progress has been made in the following two aspects: (1) spectroscopic and chemical reaction studies on the effects of drying and mild oxidation of a Wyodak subbituminous coal on its structure and pretreatment/liquefaction at 350{degrees}C; and (2) effects of dispersed catalyst and solvent on conversion and structural changes of a North Dakota lignite. Drying and oxidation of Wyodak subbituminous coal at 100-150{degrees}C have been shown to have significant effects on its structure and on its catalytic and non-catalytic low-severity liquefaction at 350{degrees}C for 30 min under 6.9 MPa H{sub 2}. Spectroscopic analyses using solid-state {sup 13}C NMR, Pyrolysis-GC-MS, and FT-IR revealed that oxidative drying at 100-150{degrees}C causes the transformation of phenolics and catechol into other related structures (presumably via condensation) and high-severity air drying at 150{degrees}C for 20 h leads to disappearance of catechol-like structure. Increasing air drying time or temperature increases oxidation to form more oxygen functional groups at the expense of aliphatic carbons. Such a clearly negative impact of severe oxidation is considered to arise from significantly increased oxygen functionality which enhances the cross-link formation in the early stage of coal liquefaction. Physical, chemical, and surface physicochemical aspects of drying and oxidation and the role of water are also discussed. A North Dakota lignite (DECS-1) coal was studied for its behaviors in non-catalytic and catalytic liquefaction. Reactions were carried out at temperatures between 250 and 450{degrees}C. Regardless the reaction solvents and the catalyst being used, the optimum temperature was found to be 400{degrees}C. The donor solvent has a significant effect over the conversion especially at temperatures higher than 350{degrees}C

Total synthesis and biological evaluation of the tetramic acid based natural product harzianic acid and its stereoisomers

Financial support for this project was provided by Cancer Research UK (Grant No. C21383/A6950)The bioactive natural product harzianic acid was prepared for the first time in just six steps (longest linear sequence) with an overall yield of 22%. The identification of conditions to telescope amide bond formation and a Lacey-Dieckmann reaction into one pot proved important. The three stereoisomers of harzianic acid were also prepared, providing material for comparison of their biological activity. While all of the isomers promoted root growth, improved antifungal activity was unexpectedly associated with isomers in the enantiomeric series opposite that of harzianic acid.Publisher PDFPeer reviewe

Reinstated p53 response and high anti-T-cell leukemia activity by the novel alkylating deacetylase inhibitor tinostamustine

Non peer reviewe

Advanced Thermally Stable Jet Fuels

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 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 from coal

Effects of low-temperature catalytic pretreatments on coal structure and reactivity in liquefaction

This work is a fundamental study of catalytic pretreatments as a potential preconversion step to low-severity liquefaction. The ultimate goal of this work is to provide the basis for the design of an improved liquefaction process and to facilitate our understanding of those processes that occur when coals are initially dissolved. The main objectives of this project are to study the effects of low-temperature pretreatments on coal structure and their impacts on the subsequent liquefaction. The effects of pretreatment temperatures, catalyst type, coal rank and influence of solvent will be examined. We have made significant progress in the following four aspects during this quarterly period: (1) influence of drying and oxidation of coal on the conversion and product distribution in catalytic liquefaction of Wyodak subbituminous coal using a dispersed catalyst; (2) spectroscopic characterization of dried and oxidized Wyodak coal and the insoluble residues from catalytic and thermal liquefaction; (3) the structural alteration of low-rank coal in low-severity liquefaction with the emphasis on the oxygen-containing functional groups; and (4) effects of solvents and catalyst dispersion methods in temperature-programmed and non-programmed liquefaction of three low-rank coals