Methane concentration increase

Figure 14.61 illustrates the much larger changes, more than 20°C from one extreme to the other, that have occurred historically when viewed over these long time periods. Associated with decreases in temperature are decreased methane concentrations, increased dust loadings, and decreased snow accumulations (e.g., see Fig. 14.62). (It should be noted that the amplitude of the temperature changes can vary from site to site for example, Dahl-Jensen et al. (1998) showed that the...

Thermodynamically, the reforming reaction. Equation 3.5.1, shows that the reformer should be operated at die lowest pressure and highest temperature possible. The reforming reaction occurs on a nickel-oxide catalyst at 880 C (1620 "F) and 20 bar, which results in a 25 "C approach to the equihbrium temperature [25,29]. Methane conversion increases by reducing the pressure, but natural gas is available at a high pressure. It would be costly to reduce the reformer pressure and then recompress the synthesis gas later to 100 bar (98.7 atm) for the converter. The steam to carbon monoxide ratio is normally in the range of 2.5 to 3.0 [30]. The ratio favors both the conversion of methane to carbon monoxide and the carbon monoxide to carbon dioxide as indicated by Equations 3.5.1 and 3.5.3. If the ratio is decreased, the methane concentration increases in the reformed gas, but if the ratio is set at three, the unreacted methane is small. The methane is a diluent in the synthesis reaction given by Equation 3.5.2. 

I do not think that we can rule out changes in OH concentration. The interconnection between methane and hydroxyl radicals is very strong. Methane removal is controlled by hydroxyl concentration hydroxyl concentration is partially controlled by methane. An increasing methane concentration should tend to lower hydroxyl concentration, a feedback system in which the methane concentration increases by a larger percentage than the increase in source strength. 

For steam gasification, lower total system pressure increased carbon conversion. However, methane concentration increased at higher system pressure. 

The previous volume measurement was done by methane because this does not react and does not even adsorb on the catalyst. If it did, the additional adsorbed quantity would make the volume look larger. This is the basis for measurement of chemisorption. In this experiment pure methane flow is replaced (at t = 0) with methane that contains C = Co hydrogen. The hydrogen content of the reactor volume—and with it the discharge hydrogen concentration— increases over time. At time t - t2 the hydrogen concentration is C = C2. The calculation used before will apply here, but the total calculated volume now includes the chemisorbed quantity. 

It was shown in laboratory studies that methanation activity increases with increasing nickel content of the catalyst but decreases with increasing catalyst particle size. Increasing the steam-to-gas ratio of the feed gas results in increased carbon monoxide shift conversion but does not affect the rate of methanation. Trace impurities in the process gas such as H2S and HCl poison the catalyst. The poisoning mechanism differs because the sulfur remains on the catalyst while the chloride does not. Hydrocarbons at low concentrations do not affect methanation activity significantly, and they reform into methane at higher levels, hydrocarbons inhibit methanation and can result in carbon deposition. A pore diffusion kinetic system was adopted which correlates the laboratory data and defines the rate of reaction. 

Effects of Cold Gas Recycle and Approach to Equilibrium. Product gases resulting from various CGR ratios were analyzed (Table XI). For the experiments tabulated, a decrease in the cold recycle ratio resulted consistently in increases in the product gas concentrations of water vapor, hydrogen, and carbon dioxide and a decrease in methane concentration. These trends may be noted in experiment HGR-12 as the CGR ratio decreased from 8.7 1 to 1.2 1, in experiment HGR-13 as it increased from 1.0 1 to 9.1 1, and in experiment HGR-14 as it decreased from 3.0 1 to 1.0 1. These trends indicate that the water-gas shift reaction (CO + H20 —> C02 + H2) was sustained to some degree. Except for the 462-hr period in experiment HGR-14, the apparent mass action constants for the water-gas shift reaction (based on the product gas compositions in Table XI) remained fairly constant at 0.57-1.6. These values are much lower than the value of 11.7 for equilibrium conversion at 400°C. In... 

This means that the observed change in M mainly reflects a change in the source flux Q or the sink function. As an example we may take the methane concentration in the atmosphere, which in recent years has been increasing by about 0.5% per year. The turnover time is estimated to be about 10 years, i.e., much less than Tobs (200 years). Consequently, the observed rate of increase in atmospheric methane is a direct consequence of a similar rate of increase of emissions into the atmosphere. (In fact, this is not quite true. A fraction of the observed increase is probably due to a decrease in sink strength caused by a decrease in the concentration of hydroxyl radicals responsible for the decomposition of methane in the atmosphere.)... 

The role of carbon dioxide in the Earth s radiation budget merits this interest in atmospheric CO2. There are, however, other changes of importance. The atmospheric methane concentration is increasing, probably as a result of increasing cattle populations, rice production, and biomass burning (Crutzen, 1983). Increasing methane concentrations are important because of the role it plays in stratospheric and... 

Problems may arise when the atmospheric concentration of greenhouse gases increases. Since the beginning of the industrial revolution, atmospheric concentrations of carbon dioxide have increased nearly 30%, methane concentrations have more than doubled, and nitrous oxide concentrations have risen by about 15%. These increases have enhanced the heat-trapping capability of the earth s atmosphere. 

Table 14.4 summarizes the estimated total direct radiative forcing calculated for the period from preindustrial times to 1992 for C02, CH4, N20, and O, (IPCC, 1996). The estimate for CH4 includes the effects due to its impacts on tropospheric ozone levels or on stratospheric water vapor, both of which are generated during the oxidation of methane. That shown for 03 is based on the assumption that its concentration increased from 25 to 50 ppb over the Northern Flemi-sphere. The total radiative forcing due to the increase in these four gases from preindustrial times to the present is estimated to be 2.57 W m 2. 

This decrease of H2 and CO, coupled with an increase in methane concentration, is attributed to deactivation of the shift catalysts and increased met-hanation reaction. However, this does not explain the increase in CO2 concentration, and it is difficult to envision that the addition of sulfur would increase the methanation activity. The reformate produced in the ATR step was not analyzed, making it difficult to interpret these results. 

The differences in reactions at different reactor positions was studied by Springmann et al. who reported product compositions for ATR of model compounds as a function of reactor length in a metal monolith coated with a proprietary noble metal containing Rh. As expected, the oxidation reactions take place at the reactor inlet, followed by the SR, shift, and methanation reactions. Figure 32 shows the product concentration profiles for a 1-hexene feed, which are typical results for all the fuels tested. These results show that steam, formed from the oxidation reactions, reaches a maximum shortly after the reactor inlet, after which it is consumed in the shift and reforming reactions. H2, CO and CO2 concentrations increase with reactor length and temperature. In this reactor, shift equilibrium is not reached, and the increase in CO with distance from the inlet is the net result of the shift and SR reactions. Methane is... 

The dewpoint of a gas is a direct function of the concentration of the various hydrocarbon components in the gas. Increasing concentrations of any hydrocarbon heavier than methane will increase the tendency of liquids to condense at some pressure-temperature condition, but small quantities of pentanes and heavier components create more liquid condensation problems than somewhat larger quantities of intermediate hydrocarbons such as butanes, propane, and ethane. The heavier the hydrocarbon, the greater will be the effect of a given quantity on the dewpoint of the gaa. 

Table 3. Base background scenarios and subsonic aircraft NOx scenarios used in the global model studies. These scenarios are used to study ozone increases, non linearity in ozone productions from aircraft emissions and the impact on methane lifetime and methane concentrations for future aircraft emissions.

At high pressure methane becomes thermodynamically stable and does not enter into endothermic reactions which are accompanied by an increase in the number of molecules. Under these conditions the flegmatizing action of excess methane proves weak. Evidently, the higher heat capacity of methane is compensated for by the increase in the chemical reaction rate for increased methane concentration. 

---