Chemistry Commons^™

The Partial Oxidation Of Methane To Methanol & Formaldehyde, Terry Matthews

Masters Theses & Specialist Projects

The conversion of methane into methanol is viewed as one approach to utilizing the vast reserves of natural gas.

One such prospect for the utilization of natural gas is the partial oxidation of methane to methanol. Methanol ranks high on the commodity market. As a liquid it is easily transportable and therefore skirts the issue of vast amounts of a gas having to be transported either by pipeline or by liquifying.

The catalytic partial oxidation of methane to methanol is investigated. Two different reactor systems are employed. The first system is a fixed bed system. The second is a fluid …

Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Analysis Of Forms Of Sulfur In Coal, Gary Ruba

Masters Theses & Specialist Projects

Methods for the determination of sulfur forms are reviewed. Each method is compared to the ASTM D 2492 standard method when data are available. The extraction of pyrites with dilute nitric acid is reviewed in detail because of its relationship to data presented in this thesis.

A new technique for the analysis of organic sulfur was developed in response to a need by the coal community for an accurate and inexpensive method. In this method nitric acid extraction is used to remove the inorganic sulfur forms and the residual coal is then analyzed for organic sulfur. Organic sulfur values obtained …

Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Administration Documents

Newsletter created by and about the WKU Chemistry department.

Alkali Extraction Test As A Predictor For Self-Heating In Coal, Arshad Parvez

Masters Theses & Specialist Projects

The self-heating of coal is a serious problem that has always affected the coal industry. Self-heating has been studied around the world for more than 100 years by many investigators, yet no accurate method of predicting self-heating in coal has been developed.

The objective of this research was to investigate the factors contributing to the self-heating in coal and to develop methods to predict the self-heating in coal and to develop methods to predict the self-heating susceptibility of various coals. A data bank containing analytical data, transportation histories, and results from laboratory tests was established at Western Kentucky University. A …

The Esterases Of The Galleria Mellonella Larvae, Salmah Juraimi

Masters Theses & Specialist Projects

Some properties of esterases of the greater wax moth larvae, Galleria mellonella (L.) were examined and the enzyme partially purified. Tris buffer was chosen as the buffer system over veronal buffer. The former causes less hydrolysis of the acetylsalicylic acid. Esterase activities were determined with acetylasalicylic acid in tris buffer (00.05 M, pH 7.85 with 0.1 M EDTA) and with acetyl-p-hydroxybenzoic acid in the same buffer. The enzyme was partially purified by combination of acetone powder preparation, ammonium sulfate precipitation, ion-exchange chromatography, and gel filtration.

The starting enzyme preparation was obtained from aceton powder preparation. The ratio of esterase activity …

The Vapor-Phase Dehydrogenation Of Ethylbenzene Using Polymeric & Polymer-Supported Quinones, Simeon Pickard

Masters Theses & Specialist Projects

Polymer-supported and polymeric quinones were synthesized and evaluated in their ability to dehydrogenate ethylbenzene in the vapor phase. The polymeric quinones were found to be more useful agents for dehydrogenation than the polymer-supported quinones, probably due to the higher concentration of quinone per given mass of polymer.

The factors that affected the yield of styrene using the polymeric quinone were the nature of the polymer, the space velocity in the column, and the reaction temperature. The space velocity was evaluated by holding constant the flow rate of the carrier gas and varying the concentration of ethylbenzene in the gas stream. …

Redox Reaction Kinetics Between Cobalt(Ii)-4,4',4",4'"-Tetrasulfophthalocyanine & Iodine In Various Solvents, Byung-Soo Yu

Masters Theses & Specialist Projects

Analyses of the kinetic data obtained on the redox reaction between cobalt(II)-4,4',4",4"-tetrasulfophthalocyanine [Co(II)TSPC4^-] and iodine in the presence of air show three reactions in dimethylsulfoxide(DMS0), N,N-dimethylacetamide(DMA), and diethylene glycol(DEG) while there are two reactions in methanol(Me0H). Two of the three reactions in DMSO, DMA, and DEG are biphasic with one reaction in all of the solvents being too fast to be accurately measured on the Cary Model 14 spectrophotometer. When the reactant solutions are purged with argon for 40 minutes under identical conditions, the same biphasic reactions are observed in DMSO and DEG while only one of the …

Characterization Of Potassium Promoted & Unpromoted Fischer-Tropsch Catalysts, Steven Miller

Masters Theses & Specialist Projects

The technique of x-ray photoelectron spectroscopy (XPS) has been applied to characterize iron-manganese catalysts used in Fischer-Tropsch synthesis. The catalysts, which vary in composition from 10 FE/90 Mn, to 50 Fe/50 Mn are analyzed after being placed in a slurry reactor and having synthesis gas reacted over them. Changes, in catalyst composition are investigated further using in situ techniques. Additionally, 20 Fe/80 Mn catalysts containing potassium in the range of 0.1 wt.% to 1.3 wt.% are analyzed in the same manner. These studies have permitted the identification of some of the factors influencing activation and deactivation, product selectivity, and surface …

Analytical Pyrolysis Of Thai Lignites, Naowarat Poolasap

Masters Theses & Specialist Projects

Samples of four different Thai lignites were utilized to study the effects of ceiling temperature and heating rate on the overall yield and product distribution by the technique of analytical pyrolysis (pyrolysis-gas chromatography). Ceiling temperatures of 450°, 550°, 650°, 750°, 850°, and 950°C, a heating rate of 500°C/sec and pyrolysis intervals of 20 seconds were investigated. The results were reported in terms of percentage high-volatile product and low-volatile product fraction, weight-loss (% by weight), and total yield (counts per milligram). One sample which showed the highest sensitivity to changing ceiling temperature was selected to study the effect of heating rate …

Predicting The Self-Heating Potential Of Coal, Seyed Mohammad Fatemi-Badi

Masters Theses & Specialist Projects

Self-heating in coal has been studied for well over one hundred years, yet there is no accurate or reliable method for predicting the potential of certain coals to undergo self-heating. Fires caused by self-heating, and eventually spontaneous combustion, have occurred in the high wall of surface mines, in underground mines, in coal stockpiles, and on trains, barges and ships. Self-heating in coal is brought about through a complex interplay of conditions depending on the specific properties of the coal as well as many external factors involved in the mining and handling of coal.

In a study supported by the United …

Hydrogenation Of Nitro Compounds To Amines Using Polymer Bound Catalysts, Eduardo Baralt

Masters Theses & Specialist Projects

A polymer bound catalyst is a relatively new type of catalyst. The basis of polymer bound catalysis lies in the chemical attachment of a homogeneous catalyst to a solid support, in our case, polystyrene. Applications of polymer bound catalysts started in the late 1960’s, and have been used in several types of reactions. In some cases such a catalyst offers a series of advantages over the classical models of catalysis, homogeneous and heterogeneous.

The hydrogenation of various aromatic and aliphatic nitro compounds, such as nitro-benzene and 2-nitropropane, were performed successfully. The hydrogenation activity in most cases was high, and in …

Co-Oxidative Depolymerization Of Coal, Renae Rosencrans

Masters Theses & Specialist Projects

In contrast to current coal conversion technology, cooxidative depolymerization of coal is a novel approach to coal liquefaction in that the reactions are carried out under relatively mild conditions. This free radical process utilizes air or oxygen and a suitable co-oxidant (solvent) which acts as a radical and hydrogen transfer agent throughout the coal matrix. Ideally, co-oxidation would lead to the formation of hydroperoxide groups at the reactive bridging sites in the coal matrix, which upon decomposition would lead to C-C bond scission.

The effects of several variables on co-oxidation and subsequent post-treatment were investigated. Up to 49% conversion to …

Impact Of Several Chemical And Physical Properties Of Two H-Coal Recycle Solvent Streams On Their Relative Solvent Quality, Joe Collins

Masters Theses & Specialist Projects

The purpose of this study was to follow the solvent quality curve of the recycle solvent streams of the H-Coal Pilot Plant run by Ashland Petroleum Company at Catlettsburg, Kentucky. This was done with the use of a microautoclave (shaker-bomb liquefaction unit). Several physical and chemical properties of these recycle oils were determined, and these values were correlated with the observed solvent quality. It is shown that the relative, solvent quality of these recycle oils correlate well with many of the chemical and some of the physical properties determined in this study.

Use Of Ft-Ir And Nmr Spectra Of The Thf Extracts Of Mid-Rank Bituminous Coals To Predict Plasticity, Samuel Adesoji Irefin

Masters Theses & Specialist Projects

Plasticity, which typically develops at 380-420°C, is a unique property of mid-ranked coals. The phenomenon of plasticity in coals has been known for a long time but is still poorly understood. Even among coals of identical subrank and chemical composition, large differences in plastic behavior are commonly encountered. Plastic coals go through a softening and swelling state upon heating before they resolidify. Concurrent with the plastic state of the coal, thermal decomposition of the coal takes place.

The coking ability of a coal can be directly related to the plasticity of the coal. In liquefaction reactions, plastic coals tend to …

The Nature Of Supported Co-Mo And Ni-W And Hydrodenitrogenation And Hydrodesulfurization Of Model Compounds, Eric Dadey

Masters Theses & Specialist Projects

The catalytic vapor-phase isomerization, hydrogenolysis, and/or disproportionation of trimethylbenzen (TMB) over Co-Mo/Al₂O₃ and Ni-W/Al₂O₃ was studied at 480°C, 400 psi reactor pressure, and a constant H₂ flow. Each catalyst was run in the reduced or sulfided form. The results show a marked difference in the product distributions for each catalyst, which is attributed to differences in the catalysts’ acidities.

The hydrodenitrogenation (HDN) of quinolone and the hydrodesulfurization (HDS) of benzothiophene were also studied. The compounds were reacted in a 1 liter autoclave at 325°C and varying partial pressures of H₂. The …

The Low-Temperature Pyrolysis Of A Nitrated North Dakota Lignite, Dennis Spears

Masters Theses & Specialist Projects

Low-temperature pyrolysis is the thermal degradation of coal in an inert atmosphere at temperatures below 700°C. Coal pyrolysis is well-studied, being a complex mix of many reactions. Pyrolysis is affected by changes in many different process variables, such as temperature, pressure and heating rate. Low-temperature pyrolysis is an old and well-studied process.

Chemical pretreatments have been used to beneficiate conversion processes, inducln pyrolysis. Nitration has not been one of them. Pyrolyzing a nitrated coal would, hopefully, rapidly devolatilize the coal and break up the matrix into more commercially usable products. The nitration procedure developed by The Standard Oil Company minimizes …

H2o2-Tfa-H2so4 Oxidation Of Coal & Coal Model Compounds, Darrell Pierce

Masters Theses & Specialist Projects

The Deno coal oxidation technique was investigated as a tool for the characterization of the aliphatic components of coal. This technique was applied to three high sulfur Kentucky coals:(1) No. 789673, (2) KCER 4002-Elkhorn No. 2, (3) KCER 7122-Ky. No. 12 and a low sulfur coal from Alpha Resources, Inc. Model compound investigations on toluene, ethyl benzene, propyl benzene, bibenzyl, indan and tetralin were also conducted. Different addition modes were investigated using ethyl benzene and diphenylmethane. The stability of the expected aliphatic acid products in the oxidation reagent were also investigated.

The data indicated the following:

1. Pyrite present in high …

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Desulfurization Of Coal Using Carboxylic Acids & Peracids, Dwight Watson

Masters Theses & Specialist Projects

Bituminous coals were desulfurized by leaching in a 325 ml, agitated, autoclave with hot, dilute solutions of carboxylic acids, buffered carboxylic acids, carboxylic salts, and carboxylic salt:alkali combinations. The partial pressure of oxygen was not increased as it was found not to increase the amount of organic sulfur removal. The effect of increasing carboxylic size and decree of desulfurization was studied. Among the carboxylic acids studied, formic acid removed the greatest amount of organic sulfur;and iso-valeric acid removed the greatest percentage of pyritic sulfur. It was found that there is a direct correlation between the amount of organic sulfur removal …

Non-Matrix Corrected Organic Sulfur Determination In Coal By Energy Dispersive X-Ray Spectroscopy, Carol Clark

Masters Theses & Specialist Projects

A method for non-matrix corrected organic sulfur analysis by energy dispersive X-ray spectroscopy has been developed using petroleum coke standards. This technique capitalizes on the fact that when a substance is excited by an electron beam it will emit photons of electromagnetic radiation in the X-ray range. The emitted X-rays are characteristic of the excited elements in the substance. Typically, electron beam microanalysis is a rapid, nondestructive analytical technique to quantitatively measure organic sulfur in coal. The results show good correlation to ASTM values for numerous well characterized bituminous coals with a wide range in total and pyritic sulfur content. …

Corrosion Of Carbon Steel In Synthetic Coal Liquid Wash Waters, Keith Evans

Masters Theses & Specialist Projects

The Potentiodynamic corrosion measuring technique is an electrochemical analytical method which measures corrosion rates of a metal exposed to a corrosive environment.

The corrosion characteristics of carbon steel A1044 in aqueous solutions of aniline hydrochloride,simulating a coal liquid wash water, were determined by this method. The effects of solution velocity and oxygen concentration on the system were also determined.

A bimodal corrosion rate effect was observed in deaerated solutions of 1000 and 5000 ppm chloride as aniline hydrochloride. This effect was interpreted to be the result of the formation of a film on the surface of the specimen.

Spontaneous Heating Of Coal & Electrochemical Measurements Of Corrosion Rates, Bihan Naderi

Masters Theses & Specialist Projects

A new and relatively fast method for measuring the susceptibility of coal to spontaneous heating was studied in this work.

This method is based on the ability of coal to adsorb iron(III) from aqueous solutions. The more iron taken up by the coal, the more susceptible the coal is to spontaneous heating. The relationship holds for most of the coals being analyzed during this research project and for other succeeding ones.

The experimental procedures used and results obtained are discussed. A brief literature survey of other applied methods which have been studied, including a description of many factors affecting the …

Analytical Pyrolysis Of Eastern Shales, Kenneth Naples

Masters Theses & Specialist Projects

The effects of pyrolysis interval, ceiling temperature, heating rate and mesh size on both the pyrolysis yield and relative product distribution for two eastern oil shales (Sunbury and Cleveland) were studied. An extension of the technique of analytical pyrolysis (pyrolysis-gas chromatography) was used. This extension employed a Chemical Data System (C.D.S.) Model 382 Extended Pyroprobe and a C.D.S. Model 310 Concentrator which enabled the pyrolysis products to be collected into a trap system. After completion of a predetermined heating interval, the trap was pulse heated to 250°C and the high and low volatile components were back-flushed into the injection port …

Soil Degradation Of H-Coal Liquid & Various Aromatic Compounds, Kevin Wilson

Masters Theses & Specialist Projects

The common bacterial genera Pseudomonas and Acinetobacter are ubiquitous in most soils and are capable of degrading a large number of chemical compounds. While the degradative pathways of several individual aromatic compounds are known, the degradative pathways of many other aromatic compounds have not yet been elucidated. In addition, very little work has been done on the microbial degradation of coal liquids in the environment.

Previous work at Western Kentucky University has shown that decomposition of Ashland Oil Company's liquified coal can indeed be accomplished by the above bacterial genera in an enriched liquid media. The topic of this thesis …

Dmf Extractability As A Predictor Of Plasticity In Bituminous Coals, Jana Whitt

Masters Theses & Specialist Projects

Plasticity is a phenomenon of certain coals that is not completely understood. Some bituminous coals go through a softening and swelling state upon heating before they re-solidify. It is this softening and swelling state that is labeled as the "plastic state" of the coal. Concurrent with the plastic state of the coal, thermal decomposition of the coal takes place. Several low molecular weight gases are also evolved. These occur at a temperature of approximately 450° C.

The plasticity of a coal is a good indication of the coking ability of a coal. Plastic coals tend to give higher yields in …

Kinetic & Spectral Studies Of Copper(Ii)-4,4',4",4'"-Tetrasulfophthalocyanine In Aqueous Solution, Stephen Scholl

Masters Theses & Specialist Projects

The monomer-dimer equilibrium of CuTSPC^4- was examined by spectral methods in aqueous solution over a total dye concentration of 2 x 10^-8M to 8 x 10^-7M at 24°C. The value obtained for the dimerization constant, KD,was 1.1 x 10⁷M^-1 which is smaller than literature values. However, the discrepancy is not appreciable considering the differences in the methods used and the experimental conditions of the different solutions. Spectral measurements of the dimerization constant were made at only one temperature since the spectral changes were quite small when the temperature was varied. This observation …

Analytical Pyrolysis Of Eastern Oil Shales, Lizbeth Sturgeon

Masters Theses & Specialist Projects

The Sunbury shale and the Cleveland member of the Ohio shale were studied utilizing the technique of analytical pyrolysis (pyrolysis gas chromatography). The effects of ceiling temperature, heating rate, and pyrolysis interval on the pyrolysis yield and relative product distribution for these eastern oil shales were observed. Carefully monitored pyrolysis of the shale allows separation of high and low volatile components and measurement of the relative peak areas in the pyrogram provides the yield of the high and low volatile fractions. Linear temperature ramps of 5000, 2000, and 100°C per second were employed. Ceiling temperatures of 450°C to 950°C and …

Kinetic And Spectral Studies Of Cobalt (Ii) -4, 4’, 4’’, 4’’’ –Tetrasulfophthalocyanine With Sodium Cyanide In Aqueous Solution, Pablo J. Diaz Cruz

Masters Theses & Specialist Projects

Kinetic studies of the cobalt (II)-4, 4’, 4’’, 4’’’-tetrasulfophtalocyanine and cyanide system were performed under argon and in air over temperature ranges of 294-314°K and 294-324°K, respectively. Two reactions were detected under argon. One was quite rapid and was followed on the stopped-flow apparatus. The results are consistent with the perturbation of a monomer-dimer equilibrium. The second reaction was slow enough to be followed spectrophotometrically on the Cary Model 14 spectrophotometer. The second order rate constant of 0.11 M^-1 sec^-1 at 294°K has been attributed to the rate of substitution of the second cyanide addition to a dye-cyanide …

Oxidation Activity Of Catalyst 3-7a Toward Formaldehyde, Hydrogen Cyanide, And Some Alkane Gases, John Kawas

Masters Theses & Specialist Projects

The activity of Catalyst 3-7A toward the oxidation of formaldehyde, hydrogen cyanide, methane, propane, and isobutene was examined at temperatures between 25°C and 400°C. The catalyst consists of palladium(II) and copper (II) salts impregnated on an alumina support. The oxidation measurements were made primarily with gas chromatographs, although form aldehyde and hydrogen cyanide were also examined using the colorimetric fushsin method and Liebig titrations, respectively. Catalyst 3-7A demonstrated appreciable activity toward the oxidation of all gases studied except formaldehyde where there was no evidence of oxidation. The latter result is quite unexpected since aldehydes are more easily oxidized than alkanes. …

Investigation Of The Role Of Phenols In Oxidative Degradation Of Coal-Derived Naphthas, Jeffrey Macke

Masters Theses & Specialist Projects

The oxidative instability of coal liquids is a possible problem for the utilization of these alternate fuels. Past experience with both petroleum and coal-derived distillates indicates that heteroatomic species are intimately involved in such degradation. However, the exact nature of the chemistry is, in many cases, unclear. The goal of this work is to study the role of phenols in the chemistry of oxidative degradation of naphthas from a variety of current conversion processes. The effects of exposure to oxygen, metal surfaces, and metal salts have been investigated in order to identify the major routes leading to gum formation.

Coal-derived …