Hydrogen by methanation

A series of kinetic studies on the carbon filament formation by methane decomposition over Ni catalysts was reported by Snoeck et al. [116]. The authors derived a rigorous kinetic model for the formation of the filamentous carbon and hydrogen by methane cracking. The model includes the following steps ... 

Fonseca, A. and Assaf, E.M. Production of the hydrogen by methane steam reforming over nickel catalysts prepared from hydrotalcite precursors. Journal of Power Sources, 2005, 142 (1-2), 154. 

In recent years, new concepts to produce hydrogen by methane SR have been proposed to improve the performance in terms of capital costs reducing with respect to the conventional process. In particular, different forms of in situ hydrogen separation, coupled to reaction system, have been studied to improve reactant conversion and/or product selectivity by shifting of thermodynamic positions of reversible reactions towards a more favourable equilibrium of the overall reaction under conventional conditions, even at lower temperatures. Several membrane reactors have been investigated for methane SR in particular based on thin palladium membranes [14]. More recently, the sorption-enhanced steam methane reforming (Se-SMR) has been proposed as innovative method able to separate CO2 in situ by addition of selective sorbents and simultaneously enhance the reforming reaction [15]. 

The production of hydrogen by methane reforming in a membrane reactor presents the following advantages ... 

Now heat the tube very gently at first and then more strongly. A non-conden-sible product such as hydrogen or methane is best detected by collecting a sample of the gas in a test-tube as shown in Fig. 71(A). A condensible product such as benzene or phenol should be collected by twisting the delivery-tube downwards and collecting the liquid in a few ml. of water in a test-tube as shown In Fig. 71(B). 

Lower alkanes such as methane and ethane have been polycondensed ia superacid solutions at 50°C, yielding higher Hquid alkanes (73). The proposed mechanism for the oligocondensation of methane requires the involvement of protonated alkanes (pentacoordinated carbonium ions) and oxidative removal of hydrogen by the superacid system. 

Any of the medium heat-value gases that consist of carbon monoxide and hydrogen (often called synthesis gas) can be converted to high heat-value gas by methanation (22), a low temperature catalytic process that combines carbon monoxide and hydrogen to form methane and water. 

As an alternative to scmbbing out the CO2 followed by methanation, the shifted gas can be purified by pressure-swing adsorption (PSA) when high purity hydrogen is desirable. 

This reaction is cataly2ed by silica, bauxite, and various metal sulfides. The usual catalyst is activated alumina, which also cataly2es the reduction by methane (228). Molybdenum compounds on alumina are especially effective catalysts for the hydrogen sulfide reaction (229). 

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. 

A typical ethane cracker has several identical pyrolysis furnaces in which fresh ethane feed and recycled ethane are cracked with steam as a diluent. Figure 3-12 is a block diagram for ethylene from ethane. The outlet temperature is usually in the 800°C range. The furnace effluent is quenched in a heat exchanger and further cooled by direct contact in a water quench tower where steam is condensed and recycled to the pyrolysis furnace. After the cracked gas is treated to remove acid gases, hydrogen and methane are separated from the pyrolysis products in the demethanizer. The effluent is then treated to remove acetylene, and ethylene is separated from ethane and heavier in the ethylene fractionator. The bottom fraction is separated in the deethanizer into ethane and fraction. Ethane is then recycled to the pyrolysis furnace. 

Exit gases from the shift conversion are treated to remove carbon dioxide. This may be done by absorbing carbon dioxide in a physical or chemical absorption solvent or by adsorbing it using a special type of molecular sieves. Carbon dioxide, recovered from the treatment agent as a byproduct, is mainly used with ammonia to produce urea. The product is a pure hydrogen gas containing small amounts of carbon monoxide and carbon dioxide, which are further removed by methanation. 

Kolbel et al. (K16) examined the conversion of carbon monoxide and hydrogen to methane catalyzed by a nickel-magnesium oxide catalyst suspended in a paraffinic hydrocarbon, as well as the oxidation of carbon monoxide catalyzed by a manganese-cupric oxide catalyst suspended in a silicone oil. The results are interpreted in terms of the theoretical model referred to in Section IV,B, in which gas-liquid mass transfer and chemical reaction are assumed to be rate-determining process steps. Conversion data for technical and pilot-scale reactors are also presented. 

A composite film of SiC and diamond was produced from tetramethylsilane, hydrogen, and methane in a microwave plasma on single-crystal silicon wafers. Volume fraction of the components can be adjusted by varying the gas composition. 

Subsequently, the problem was investigated by Karpov and Severin [6]. They used closed vessels with a diameter of 10cm and 10, 5, and 2.5cm width, initially at atmospheric pressure. The vessels were filled with different lean hydrogen and methane/air mixtures and rotational speeds in the range of 130-4201/s were employed. They also included data from the study of Babkin et al. [3] in their analysis. Unfortunately, they did not observe the flame itself and measured only the pressure rise in the vessel, which was compared with pressure development in the vessel without rotahon, to draw a conclusion with respect to flame speeds and quenching. 

After peroxide injection, conversion of methane increases fix)m -4% to -10%, methanol production increases 17 fold, and carbon dioxide increases 5 fold, along with modest increases in hydrogen and carbon monoxide. Introduction of hydroxyl radicals to the reactor leads to a greater fi action of product going to methanol as evidenced by methane conversion increasing 2.5 times, whereas methanol production increases 17 times. The increase in carbon dioxide is fiom "deep" oxidation of... 

Let us now use the sequence of elementary steps to explain the activity loss for some of the catalysts The combination of hydrogen chemisorption and catalytic measurements indicate that blocking of Pt by coke rather than sintering causes the severe deactivation observed in the case of Pt/y-AljOj The loss in hydrogen chemisorption capacity of the catalysts after use (Table 2) is attributed mainly to carbon formed by methane decomposition on Pt and impeding further access. Since this coke on Pt is a reactive intermediate, Pt/Zr02 continues to maintain its stable activity with time on stream. 

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