Conversion of bituminous coal in COH2O systems: 2. pH Dependence

Under $\text{CO}\text{H}{}_2\text{O}$ systems at initial pH values s> 12.6, an Illinois No. 6 coal, PSOC-26, was converted to a fully pyridine-soluble product, with benzene and hexane solubilities of 50% and 18%, respectively. The product gases were H₂ and CO₂. However, the expected $\text{H}{}_2\text{CO}{}_2$ ratio of 1.0 based on the water gas shift reaction was not observed, but the deficit in hydrogen was found in the increased hydrogen content of the coal product. 95% coal carbon recovery and good hydrogen balances were obtained, and the coal products were found to be very similar to those from conventional tetralin systems. The results suggest an efficient base-catalysed process, and that $\text{CO}\text{H}{}_2\text{O}$ systems are useful for coal studies.     

High-temperature 1H n.m.r. study of oxidized coal

Two coking coals, a caking and a non-caking coal are examined in a Bruker pulsed ¹H n.m.r. spectrometer in the temperature range 293–730 K. One coking and the caking coal are oxidized in air at 383 K for 13 days. Temperatures of signal appearance and loss are noted as well as the temperatures of minimum signal half-peak width ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$). There occurs no change in the above three temperatures with oxidation of the coals. The variation of ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) with temperature of the coal is also measured. Changes in ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) are more pronounced for the caking coal. The softening and solidification temperatures are below and above, respectively, those reported using the Gieseler method. Values of ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) increase beyond the minimum value as the fluidity continues to increase. This may be caused by an increase in average molecular weight of constituent molecules and/or an increasing concentration of free radicals in the fluid phase. This experimental approach may afford a new method to characterize coals which are to be used in liquefaction processes.     

Activated diffusion of methane from coals at elevated pressures

Diffusion of methane from three coals ranging in rank from anthracite to HVA bituminous has been studied at initial methane pressures up to about 2.76 MPa (400 psi). Unsteady-state diffusion conditions existed, the methane pressure within the coal particle decreasing with time while the methane pressure outside the particles remained at atmospheric. The diffusion parameter $\text{D}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{r}{}_0$ increased with increasing methane concentration at high values of methane sorption. Diffusion was activated but the exact magnitude of the activation energy is uncertain owing to the suspected contribution of the heat of sorption to the temperature coefficient. $\text{D}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{r}{}_0$ increased with decreasing particle size of coal studied, but r₀ is clearly less than the particle radius.     

Dielectric constants of coal-water slurries at 750 MHz

Measurements of the real portion of the dielectric constant of coal-water slurries at 750MHz are reported. Slurries of 40–65wt% of either Illinois No. 6, Utah bituminous or Texas lignite coals over the temperature range 11–71 °C were studied. The dielectric constant was independent of coal type and particle size within experimental error. The measured values of dielectric constants agreed with those predicted by the Looyenga equation: $\text{?′}\text{= [?′}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}{}_2\text{+ φ(?′}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}{}_1\text{??′}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}{}_2\text{)]}{}^3$ where: $\text{?′}$, the mean value of the dielectric constant; ?′₁, the dielectric constant (3.8) of the dry coal; ?′₂, the dielectric constant of water; φ, the volume fraction of coal.     

Macerals in bituminous coals and the coking process: 2. Coal mass properties and coke mechanical properties

Bituminous coals produced in the Ostrava-Karviná coal basin show considerable variation in their maceral composition, vitrinite reflectance and fluidity. There is a close association of the latter with the $\text{H}\text{O}$ atomic ratio expressing the different chemico-structural properties of vitrinites of lower coalification. These properties of the coal mass all influence the coke mechanical properties; moreover the $\text{H}\text{O}{}_{\mathrm{at}}$ parameter is of principal importance to the course of the coking process. Laboratory, pilot-plant and full-scale experiments show that coals rich in inertinite may give cokes of suitable mechanical properties, providing the $\text{H}\text{O}{}_{\mathrm{at}}$, ratio and the bulk density are high enough. It should be noted, however, that these coals contain finely dispersed inertinite in the vitrinite mass and this may have a positive effect on the coke mechanical properties.     

Thermoplastic properties of coal at elevated pressures: 1. Evaluation of a high-pressure microdilatometer

Thermoplastic behaviour of a Pittsburgh seam hvA coal (PSOC1099) was characterized by the use of a high-pressure microdilatometer. Phenomena such as softening, swelling, final resolidification, and the temperatures at which they occur were measured as functions of heating rate (25 ° and 65 °C min^?1), particle size (= 75 μm and 250 × 425 μm), gaseous atmosphere (N₂, H₂, $\text{CO}\text{H}{}_2$) and applied gas pressure (atmospheric to 2.8 M Pa). The results obtained illustrate several important aspects of thermoplastic properties of this coal under the conditions utilized. It is observed that pressure alone can play a major role in determining its overall thermoplastic behaviour. Compared to that at atmospheric pressure, swelling is significantly reduced at 2.8 MPa of pressure for any given heating rate or particle size. In these experiments, the chemical composition of the gaseous atmospheres ($\text{CO}\text{H}{}_2$, H₂ and N₂) does not appear to alter significantly the plastic phenomena at any given pressure. Increasing the heating rate or decreasing the particle size results in increased swelling at all applied pressures and atmospheres.     

Chemical beneficiation of coal with aqueous hydrogen peroxide/sulphuric acid solutions

The removal of sulphur and ash from coal treated with aqueous hydrogen peroxide/sulphuric acid solutions has been studied at ambient temperature, under a variety of experimental conditions. Almost complete elimination of the sulphate and the pyritic sulphur was observed in most cases, as well as substantial reduction in the ash content. The other components of the organic coal matrix were not affected to a significant extent, indicating high selectivity of the $\text{H}{}_2\text{O}{}_2\text{H}{}_2\text{SO4}$ system towards sulphur oxidation. An optimal H₂SO₄ concentration was established, above which the acid was found to have an adverse effect on the oxidation of pyrite by hydrogen peroxide.     

Conversion of bituminous coal in COH2O systems: 3. Soluble metal catalysis

The oxyanions of the highest oxidation states of several transition metals, including W, Mo, Cr and Mn, were found to catalyse the liquefaction of Illinois No. 6 coal in $\text{CO}\text{H}{}_2\text{O}$ systems at 400°C. Unlike the high pH (s> 12) required in the base-catalysed system, the effective range for these metal-mediated conversions extend down to pH < 5.0. The benzene-soluble product was found to have a higher $\text{H}\text{C}$ ratio than the starting coal, and the metals were reduced to water-insoluble, lower oxidation states during conversion. A chain scheme is suggested as an explanation for the data.     

Studies of a CuY zeolite as a redox catalyst

The stability and behavior of CuY in the redox cycles with $\text{CO}\text{O}{}_2$, $\text{H}{}_2\text{O}{}_2$, and $\text{CO}\text{NO}$ have been studied using a microbalance operating in the flow mode and with a standard (BET) volumetric system. When CO was used as a reducing agent CO₂ was produced, thus removing oxygen from the zeolite lattice, but when H₂ was used only some of the H₂ consumed was evolved as H₂O. The rest was retained as lattice OH groups, but this was minimal when H₂ was used after treating the sample with CO. Oxidation with NO produced only N₂. At 500 °C the sample was stable and could be reversibly oxidized and reduced through many cycles using either $\text{CO}\text{O}{}_2$ or $\text{NO}\text{CO}$. In all cases the ratio $\text{O}\text{Cu}$ was close to 0.5, i.e., $\text{1e}\text{Cu}$. Treatment in CO at higher temperatures did not affect the reversible nature of the oxidation, but now the valence change was substantially larger; it approached $\text{2e}\text{Cu}$. The crystallinity of the exchanged zeolite was studied using X-ray diffraction and by measurement of the pore filling with liquid N₂. No significant changes could be detected after the different treatments, even those performed at 750 °C. Temperature-programmed reduction, temperature-programmed oxidation, and X-ray diffraction studies were made and the different maxima are reported. CuO and Cu ^o appeared in the oxidized and reduced samples, respectively, after treatment at 750 °C in CO but not at lower temperatures. Subsequent redox cycles at 500 °C did not appear to affect the size or amount of Cu ^o crystallites. CuY was active in the oxidation of CO with O₂ or NO. Its activity was lower than that of FeY zeolite when it exhibited an oxygen-carrying capacity of 0.5 $\text{O}\text{Cu}$. Treatment with CO at 750 °C, however, reversed the situation. Kinetic results showed that the fresh CuY catalyst was close to zero order in CO and fractional order in O₂ with an activation energy of 15 kcal/mole. After treatment at 750 °C in CO, the rate law became dependent upon the $\text{CO}\text{O}{}_2$ ratio. It was close to first order in CO and zero order in O₂ under oxidizing conditions ($\text{CO}\text{O}{}_2\text{≤ 2}$), but the orders were reversed under reducing conditions ($\text{CO}\text{O}{}_2\text{> 2}$). The activation energies were 12 and 15 kcal/mole, respectively. The data suggested that the Cu²⁺ with bound oxygen are the species active in the oxidation reaction.     

Mineral matter as a measure of oxidation of a coking coal

The petrography, agglomerating characteristics, low-temperature ash (LTA) mineralogy and chemistry of ten consecutive channel samples from D seam, Natal Ridge, Crowsnest coalfield, British Columbia, were compared. It was found that there is a direct correlation between oxidation, as indicated by absence or limited caking character, and the presence of the mineral bassanite ($\text{CaS0}{}_4\text{·}\text{1}\text{2}\text{H}{}_2\text{O}$) in LTA. An attempt to estimate quantitatively the extent of oxidation by the anhydrite content in LTA samples further heated to 500 °C has resulted in the detection of partial oxidation of a coal sample having an FSI of $\text{6}\text{1}\text{2}$, reduced from a normal value of 8. The recognition and quantification of oxidation using epigenetic gypsum and its derivatives, however, probably only applies to the weakly pyritic, usually freshwater, coals typical of the Rocky Mountain coalfields of British Columbia and the Gondwana coalfields of the southern hemisphere.     

A mechanistic study of hydrogenation of coal. 2.

In Part 1 the authors reported that liquefaction of coal by hydrogenation in the presence or absence of vehicle and with or without catalyst progresses with characteristic variations of the reaction order. In the present paper, the roles of temperature, hydrogen, vehicle and catalyst have been studied using a free-radical scavenger such as p-benzoquinone or iodine. Based on these results, a set of characteristic reactions has been identified from which the following overall rate equation has been derived: $\text{d[P}{}_{\mathrm{m}}\text{]}\text{dt}\text{= β}{}_1\text{[C] + β}{}_2\text{[C]}{}^2\text{+ β}{}_3$ where [P_m] denotes gas, and benzene-soluble products, [C] represents the percentages of organic matter in coal and benzene insoluble intermediates, and β₁, β₂ and β₃ are constants. The rate equation thus explains the experimentally observed variation of the reaction order, which depends on the predominance of a particular group of reactions. It has been postulated that pyrolysis is the main driving force, and that hydrogenation of coal either with gaseous hydrogen or by hydrogen-donating vehicle is basically influenced by reactions involving free radicals.     

Oxidation of hydrogen sulfide over microporous carbons

Microporous carbon of high purity was produced by the carbonization of Saran at 900° followed by activation in either CO₂ at 900°, O₂ at 300°, or air at 425°. The activated carbons were characterized using N₂ adsorption at ?195° CO₂ adsorption at 25°, and mercury and helium displacements. Hydrogen sulfide oxidation (at H₂S pressures between 0.4–3.8 Torr) by O₂ (in excess of stoichiometric amount) was studied between 100–160° using a microbalance, that is by weighing the build-up of sulfur on the carbon. The predominant reaction, $\text{H}{}_2\text{S +}\text{1}\text{2}\text{O}{}_2\text{→}\text{1}\text{2}\text{S}{}_2\text{+ H}{}_2\text{O}$ was first order in H₂S concentration and independent of O₂ concentration. The rate was only slightly reduced by sulfur build-up to at least 36%, by weight, on the carbon. The oxidation rate was significantly higher over the O₂-activated carbon than over the CO₂-activated carbon. Throughout the studies, oxidation rates could be correlated with area active to O₂ chemisorption. It is concluded that H₂S oxidation proceeds via rapid dissociative chemisorption of oxygen on carbon sites followed by reaction with H₂S. Rates of H₂S oxidation were also studies over commercial, granular activated carbons of significant ash contents.     

Use of oxygen isotope exchange in CO2 to characterize active sites

The characterization of carbon surface activity in the absence of gasification was attempted using oxygen isotope exchange in CO₂ over spectroscopically pure natural graphite, the surface activity being characterized by the rate of approach to isotopic equilibrium. The probable mechanism of exchange is via the first step in the carbon-CO₂ reaction, the dissociation of CO₂ over a carbon free site: $\text{CO}{}_2\text{+}\text{C}{}_{\mathrm{f}}\text{?}\text{i}{}_1\text{j}{}_1\text{C(O)}\text{+}\text{CO}$. Assuming this mechanism to hold for isotopic exchange, the theoretical rate equation was derived. The rate constants i₁, and j₁, were obtained from previous studies. Theoretical calculations show that the exchange rate is negligible over natural graphite at temperatures much below gasification conditions. Experimental verification of the theoretical analysis was not possible due to the activity of the quartz boat, holding the graphite, for catalyzing the exchange reaction. The exchange reaction was successfully followed over the Pt and CaO supported on a graphitized carbon black, in which case the activity was much, much greater than that ovgr the empty quartz boat.     

Redispersion of supported platinum catalysts

The redispersion of platinum on γ-Al₂O₃, SiO₂, and TiO₂ is experimentally studied by means of hydrogen chemisorption, X-ray diffraction, transmission electron microscopy, temperature-programmed reduction, and cyclohexene hydrogenation reaction. The increase in dispersion following treatment in oxygen below 600 °C occurs only for $\text{Pt}\text{γ-Al}{}_2\text{O}{}_3$. For $\text{Pt}\text{TiO}{}_2$, only the presence of chlorine during oxidation brings about a significant redispersion. For $\text{Pt}\text{SiO}{}_2$, redispersion does not occur under any condition. Redispersion can occur only in the presence of platinum oxide which could be stabilized by forming a complex with the support. The method for determining whether or not redispersion will occur for any systems and the conditions needed for redispersion are discussed.     

Dependence of the kinetics of the low-temperature water-gas shift reaction on the catalyst oxygen activity as investigated by wavefront analysis

The systematic investigation by means of wavefront analysis of the dependence of the microkinetics of the water-gas shift reaction on the oxidation state of a $\text{CuO}\text{ZnO}$ industrial catalyst is reported. The catalyst was pretreated for a long period of time in a mixture of H₂O, H₂, and N₂ at definite $\text{ψ =}\text{P}\text{H}{}_2\text{O}\text{P}\text{H}{}_2$ ratios, from ψ = 0.1 to ψ = 10.0 and at 230 °C. The fitting procedure at different ψ levels suggested a three-path reaction model consisting of two formal Eley-Rideal-type mechanisms which are relevant for the microkinetic shift conversion through adsorption intermediates of CO and H₂O, and a redox mechanism which regulates the oxygen activity on the catalyst surface and accounts for the interaction catalyst/reaction medium. In this investigation, an Elovich-type rate dependence of the redox mechanism has been suggested.     

Characterization of organic fractions in solvent-refined coal by quantitative n.m.r. spectroscopy

A solvent-refined coal product obtained from Pittsburgh No. 8 coal has been preparatively separated into four sized fractions by gel permeation chromatography. Quantitative ¹H and ¹³C Fourier-transform nuclear-magnetic-resonance results for the separated fractions are reported along with elemental and molecular weight analysis data. Observed trends for several average molecular parameters for these fractions (e.g. $\text{(}\text{H}\text{C}\text{)}{}_{\mathrm{alp}}$, $\text{(}\text{H}\text{C}\text{)}{}_{\mathrm{aro}}$, etc.) are discussed. The absence of certain organic functional groups, such as carbonyls, is also noted.     

Carbon as a catalyst in oxidation reactions and hydrogen halide elimination reactions

Carbon catalyses many reactions, mainly oxidation reactions with oxygen and with halogens, e.g. $\text{SO}{}_2\text{+}\text{1}\text{20}{}_2\text{→ SO}{}_3$, or CO + Cl₂→ COCl₂. It is known, however, that different carbons behave quite differently in the reduction of oxygen on fuel cell cathodes. Therefore the catalytic activity of carbons has been studied in other reactions. A convenient test reaction is the oxidation of dilute aqueous sulphurous acid. It became apparent that all catalytically active carbons contain small quantities of nitrogen, and inactive carbons such as wood charcoal or carbon blacks can be rendered highly active by treatment with N H₃ or HCN at elevated temperatures. Photoelectron spectra indicate that the catalytic activity increases parallel to the incorporation of a nitrogen species which is pyridine-like, i.e. incorporated in the aromatic layers. Treatment with NH₃ at 900 °C leads also to massive gasification of the carbons, increasing their surface area. Other reactions studied included the oxidation of aqueous oxalic acid and of methanol to formaldehyde. A quite different type of reaction is the elimination of hydrogen chloride from 1-chloroalkanes, e.g. 1 -chlorobutane. Again, activity changes in parallel to nitrogen content. Reaction products are olefins, dimers of the alkyl groups, and a polymer on the catalyst surface. The formation of alkyl dimers, e.g. n-octane in the case of n-butylchloride, suggests that radicals are involved in the reaction.     

Effects of gas environment on mineral reactions in Colorado oil shale

The effects of various sweep gases (N₂, CO₂, and H₂O) on the decomposition and reaction of calcite and dolomite (ankerite) in Colorado oil shale is reported. The disappearance of reactants and formation of products in the temperature range of 500 to 900 °C is monitored by using powder X-ray diffraction. The results show that, over this temperature range, the effect of gas environment on the rate of silicate formation follows the order $\text{H}{}_2\text{O}\text{s}\text{?}\text{>}\text{CO}{}_2\text{s}\text{?}\text{>}\text{N}{}_2$. The ‘final’ silicate-product phases are observed to be a mixture of melilite, diopside, and merwinite. Global reaction kinetics are developed that describe the rate of CO₂ evolution during decomposition of dolomite and calcite in the presence of various partial pressures of steam. Such data are useful in numerical models of oil shale retorting. Finally, the implications of these results on processing and on environmental aspects of oil shale retorting are discussed.