An investigation of the comparative reactivities of ethane and ethylene in the presence of oxygen over Li/MgO and Ca/Sm2O3 catalysts in relation to the oxidative coupling of methane

In order to examine the importance of the further oxidation of the desired C2 products in the oxidative coupling of methane, ethylene and ethane have been added to the feed (containing methane and oxygen) to a Li/MgO or Ca/Sm2O3 catalyst. The results of these measurements show that neither of these C2 molecules is stable under these conditions with either of the catalysts. Additionally, the rates of the oxidation of ethane and of ethylene alone have been measured using a gradientless reactor for both catalysts as well as for a quartz bed. It was found that the Ca/Sm2O3 material had higher activities for the oxidation of C2H6 and C2H4 (and also of CH4) than had the Li/MgO material. These higher activities result in a lower optimal reaction temperature for the oxidative coupling of methane and are (at least partially) responsible for the lower selectivity to C2 products observed with the Ca/Sm2O3 catalyst compared to that with the Li/MgO catalyst

The effect of Nb2O5 and ZrO2 additions on the behaviour of Li/MgO and Li/Na/MgO catalysts for the oxidative coupling of methane

Incorporation of Nb2O5 or ZrO2 into both Li/MgO and Li/Na/MgO systems produced ternary and quaternary catalysts, respectively, capable of attaining optimal C2 yields and selectivities at lower temperatures relative to the unpromoted materials. The degree of enhancement effected by these metal oxide additives was compared to that produced by Li/MgO and Li/Na/MgO catalysts promoted with SnO2 or Co3O4. At reaction temperatures < 700°C, the Li/Co/MgO ternary system showed marked differences in behaviour compared to the other ternary catalysts tested. This was particularly evident in the variation in C2 selectivity with time on stream during ageing studies of (i) untreated materials, (ii) materials pretreated in CO2, and (iii) materials dosed periodically with CHCI3

Kinetic and mechanistic aspects of the oxidative coupling of methane over a Li/MgO catalyst

The rate of reaction of methane with oxygen in the presence of a Li-doped MgO catalyst has been studied as a function of the partial pressures of CH4, O2 and CO2 in a well-mixed reaction system which is practically gradientless with respect to gas-phase concentrations. It is concluded that the rate determining step involves reaction of methane adsorbed on the catalyst surface with a di-atomic oxygen species. The adsorption of oxygen is relatively weak. Carbon dioxide acts as a poison for the reaction of methane with oxygen, this probably being caused by competitive adsorption on the sites where oxygen (and possibly also methane) adsorbs

Lithium chemistry of lithium doped magnesium oxide catalysts used in the oxidative coupling of methane

Active sites are created on the surface of a Li/MgO catalyst used for the selective oxidation of methane by the gradual loss of carbon dioxide from surface carbonate species in the presence of oxygen. Decomposition of the carbonate species in the absence of oxygen is detrimental to the activity of the catalyst. The active sites created are not stable but disappear either as a result of reaction with SiO2 to form Li2SiO3 or by the formation and subsequent loss of the volatile compound LiOH. In general the addition of water to the gas feed is detrimental to the stability of the catalyst. In the case of Li2CO3 strongly bonded on the surface of Li/MgO catalyst, the decomposition of the carbonate and thus the initial activity, can be enhanced by the addition of water to the gas feed. The addition of carbon dioxide to the gas feed results in a poisoning of the catalyst, the degree of this poisoning depending on the activity of the catalyst. The deactivation of the catalyst can be retarded if low concentration of carbon dioxide are added to the reaction mixture. It is possible to improve the stability of the catalyst by periodic reversal of the direction of flow of the gas steam

Oxidative coupling of methane over Ba/CaO catalysts: a comparison with Li/MgO

A comparison has been made of the behaviour in the oxidative coupling of methane of a Ba/CaO catalyst with that of a Li/MgO material. Doping of CaO with BaCO3 resulted in a catalyst which is more active at lower reaction temperatures than is BaCO3. The active oxygen entity in the case of Ba/CaO is probably an O2−2 species. Ba/CaO is more stable but less selective than is Li/MgO. The effect of residence time was studied for both Ba/CaO and Li/MgO. The direct oxidation of methyl radicals to give carbon monoxide and carbon dioxide plays a more important role in the case of Ba/CaO than is the case with Li /MgO

A study of the kinetics of the oxidative coupling of methane over a Li/Sn/MgO catalyst

The rate of reaction of methane with oxygen in the presence of a Li/Sn/MgO catalyst has been studied as a function of the partial pressures of CH4, O2 and CO2 using a well-mixed reaction system which is practically gradientless with respect to gas-phase concentrations. It is concluded that the rate-determining step involves reaction of a molecule of CH4 adsorbed on the catalyst surface with an adsorbed di-atomic oxygen species. The kinetics are consistent with a Langmuir-Hinshelwood type mechanism involving competitive adsorption of CH4, O2 and CO2 on a single site. A comparison is made with previously published results for the Li/MgO material

The selective oxidation of methane to ethane and ethylene over doped and un-doped rare earth oxides

A comparison has been made of the behaviour in the oxidative coupling of methane of the oxides of Sm, Dy, Gd, La and Tb with that of a Li/MgO material. All but the Tb4O7 (which gave total oxidation) were found to give higher yields than the Li/MgO material at temperatures up to approaching 750°C but the Li/MgO system gave better results at higher temperatures. The cubic structure of Sm2O3 was found to be responsible for its good performance while the monoclinic structure was relatively inactive and unselective. The addition of Na or Ca to cubic Sm2O3 gives a higher optimum C2 yield than that of unpromoted Sm2O3. Sm2O3 and Ca/Sm2O3 catalysts are more stable than Li/MgO, Li/Sm2O3 or Na/Sm2O3. The addition of Li or Na to Sm2O3 causes the structure to change from cubic to monoclinic; the deactivation of the Na/Sm2O3 catalysts is caused by a loss of Na coupled with the formation of the monoclinic form of Sm2O3

Iron ochre: a pre-catalyst for the cracking of methane

Background: Iron ochres are gelatinous sludges which can cause problems in terms of water management. In this manuscript, the application of iron ochre obtained from a river has been applied to catalytically crack methane – another potential waste product - into two useful products, hydrogen and a magnetic carbon containing composite.&lt;p&gt;&lt;/p&gt; Results: The powder XRD pattern of the iron ochre was found to be consistent with the expected 2-line ferrihydrite and EDX analysis showed Fe to be a major component although some Si was present. The sample was observed to contain a fraction with a tubular morphology consistent with the presence of extra-cellular biogenic iron oxide formed by leptothrix. Upon exposure to methane at elevated temperatures, the material was found to transform into an active catalyst for hydrogen production yielding a magnetic carbon containing composite material comprising filamentous carbon and encapsulating graphite.&lt;p&gt;&lt;/p&gt; Conclusion: The application of two waste products – iron ochre and methane – to generate two useful products – hydrogen and a magnetic carbon containing composite- has been demonstrated. Furthermore, the ochre has been shown to comprise tubular morphology extra-cellular biogenic iron oxide which may be of interest in terms of other applications.&lt;p&gt;&lt;/p&gt

Neuropsychological and psychiatric functioning in sheep farmers exposed to low levels of organophosphate pesticides

The aim of this thesis is to determine whether exposure to low levels of organophosphate pesticides (OPs) causes neuropsychological or psychiatric impairment. The thesis is arranged in three parts. Part 1 provides an introduction to neurotoxicology, the role of the psychologist, and the toxicity of OPs; Part 2 provides a historical review of the existing scientific evidence regarding the impact on human health of low level exposure to organophosphate pesticides. A major unresolved issue in the toxicity literature is whether repeated, low level exposure to OPs, in the absence of a history of acute toxicity, is harmful to human health. Part 3 presents the findings of a four year empirical study designed to address this issue. A cross-sectional study was undertaken in which the performance on neuropsychological tests of 127 sheep farmers with a history of low level exposure to organophosphate pesticides was compared with 78 nonexposed healthy volunteers (rural police workers) matched for age, gender, years in education and level of intelligence. Methodological weaknesses of earlier studies were addressed in the study design, such as inclusion of study participants who had retired on ill health grounds to take account of the ‘healthy worker effect’; exclusion of study participants with a history of acute poisoning and those with a psychiatric or medical history that might otherwise account for ill health; and exploration of factors that may render some individuals more vulnerable to the effects of OPs than others (e.g. genetic differences in the capacity to metabolise and detoxify OPs). In the final chapter the findings are summarised and discussed, the study design is critically appraised and the implications of the findings are listed along with recommendations for future research