Partial oxidation of methane to methanol-comparison of heterogeneous catalyst and homogeneous gas phase reactions

Potential catalysts for the partial oxidation of methane to methanol have been synthesised and tested in high pressure annular reactors. Uranium oxide and molybdenum oxide catalysts and iron sodalite catalyst have been tested under the conditions reported in the patents and under conditions which allow comparison with reactions carried out in the gas phase. None of the catalysts tested showed an improvement on the gas phase results. It was found that the oxidative nature of the metal oxide catalysts is an inherent feature which reduces the selectivity to methanol.     

Desulphurization of coals and chars by treatment in various atmospheres between 400 and 600 °C

Desulphurization of fifteen US coals of rank ranging from anthracite to sub-bituminous B and five high-temperature chars by carbon monoxide and other gases and gas mixtures between 400 and 600 °C has been studied. The sulphur content of the parent coals ranged between 3.0 and 7.3% and that of the chars between 1.3 and 3.8% by weight. A comparison between air, nitrogen, carbon monoxide, and steam-carbon monoxide mixtures as desulphurizing gases shows the order of desulphurizing ability as

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Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.     

Abstracts

Journal of the American Oil Chemists' Society -     

A microfluidic device for thermal particle detection

We demonstrate the use of heat to count microscopic particles. A thermal particle detector (TPD) was fabricated by combining a 500-nm-thick silicon nitride membrane containing a thin-film resistive temperature detector with a silicone elastomer microchannel. Particles with diameters of 90 and 200 μm created relative temperature changes of 0.11 and ?0.44 K, respectively, as they flowed by the sensor. A first-order lumped thermal model was developed to predict the temperature changes. Multiple particles were counted in series to demonstrate the utility of the TPD as a particle counter.     

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.     

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.     

How In-Home Technologies Mediate Caregiving Relationships in Later Life

In-home technologies can support older adults' activities of daily living, provide physical safety and security, and connect elders to family and friends. They facilitate aging in place while reducing caregiver burden. One of older adults' primary concerns about in-home technologies is their potential to reduce human contact, particularly from cherished caregivers. In this exploratory in situ study, we provided an ecosystem of networked monitoring technologies to six older adults and their caregivers. We analyzed the amount and content of communication between them. The amount of noncomputer-mediated communication did not decrease through the 6-week study. The content of communication coalesced into four themes: communication about the technologies, communication facilitated by technologies, intrusiveness of technologies, and fun and playfulness with the technologies. Results suggest that in-home technologies, designed with sensitivity to older adults' primary motivations, have the potential to shape and tailor important relationships in later life.