Methane synthesis problem

A significant feature of the operation of the two plants is that only a small deviation in feed gas composition is tolerable when using a stoichiometric gas. Greater deviations in the H2/CO ratio and in the residual C02 content of the feed gas will cause serious problems regarding SNG specifications. Thus, methanation of a stoichiometric synthesis gas is reasonable only when there are no stringent requirements for SNG specification. 

These tests demonstrated that the Lurgi Rectisol process provides an extremely pure synthesis gas which can be charged directly to the metha-nation plant without problems of sulfur poisoning of the nickel catalyst. However, in order to cope with a sudden sulfur breakthrough from Rectisol as a result of maloperation, a commercial methanation plant should be operated with a ZnO emergency catchpot on line. 

Dr. Moeller A methanation plant does not have a problem of selectivity. Whether you operate at low or high temperature, when using a nickel catalyst you will form only methane and no higher hydrocarbon. But with the Fischer-Tropsch synthesis, you have a wide range of possible products which can be formed. If you want to have a certain product, you must keep your temperature at a certain constant value. 

Oxygen-containing molecules cannot be tolerated in the ammonia synthesis, primarily because they form iron oxide that blocks the active surface. First the CO2 is removed, through a scrubber, by reaction with a strong base. The remaining CO (and CO2) is then removed by the methanation reaction, converting the CO into methane and water. Finally the water is removed by, for example, molecular sieves. Methane does not present problems because it interacts weakly with the catalyst surface. The gas mixture (Tab. 8.6) is compressed to the roughly 200 bar needed for ammonia synthesis and admitted to the reactor. 

Concerning the reaction pathway, two routes have been proposed the sequence of total oxidation of methane, followed by reforming of the unconverted methane with CO2 and H2O (designated as indirect scheme), and the direct partial oxidation of methane to synthesis gas without the experience of CO2 and H2O as reaction intermediates. The results obtained by Schmidt and his co-workers [4, 5] indicate that the direct reaction scheme may be followed in a monolith reactor when an extremely short contact time is employed at temperatures in the neighborhood of 1000°C. However, the majority of previous studies over numerous types of catalysts show that the partial oxidation of methane follows the indirect reaction scheme, which is supported by the observation that a sharp temperature spike occurs near the entrance of the catalyst bed, and that essentially zero CO and H2 selectivity is obtained at low methane conversions (<25%) where oxygen is not fully consumed [2, 3]. A major problem encountered... 

Ketenes rarely produce [3+ 2]-cycloaddition products with diazo compounds. The reaction possibilities are complex, and nitrogen-free products are often obtained (5). Formation of a cyclopropanone represents one possibihty. Along these lines, the synthesis of (Z)-2,3-bis(trialkylsilyl)cyclopropanones and (Z)-2-trialkylsilyl-3-(triethylgermyl)cyclopropanones from diazo(trialkylsilyl)methanes and appropriate silyl- or germylketenes has been reported (256,257). It was found that subsequent reaction of the cyclopropanone with the diazoalkane was not a problem, in contrast to the reaction of diazomethane with the same ketenes. The high cycloaddition reactivity of diazomethylenephosphoranes also extends to heterocumulenes. The compound R2P(C1)=C=N2 (R = N(/-Pr)2) reacts with CS2, PhNCO and PhNCS to give the corresponding 1,2,3-triazole derivative (60). 

The methanation reaction is a highly exothermic process (AH = —49.2 kcal/ mol). The high reaction heat does not cause problems in the purification of hydrogen for ammonia synthesis since only low amounts of residual CO is involved. In methanation of synthesis gas, however, specially designed reactors, cooling systems and highly diluted reactants must be applied. In adiabatic operation less than 3% of CO is allowed in the feed.214 Temperature control is also important to prevent carbon deposition and catalyst sintering. The mechanism of methanation is believed to follow the same pathway as that of Fischer-Tropsch synthesis. 

In a steam reforming process that includes CO shift conversion and CO2 removal, the synthesis gas still contains 0.1% to 0.2 mole % CO and 100 to 1000 ppmv of CO2. The simplest method for eliminating these small concentrations of oxygen compounds is shown by the reactions in Eqs. (5.13) and (5.17) (that are the reverse of the methane reforming process). The methane that is formed does not cause any problems in the downstream ammonia process. The methane simply acts as an inert diluent70. 

Sulfur poisoning is a key problem in hydrocarbon synthesis from coal-derived synthesis gas. The most important hydrocarbon synthesis reactions include methanation, Fischer-Tropsch synthesis, and methanol synthesis, which occur typically on nickel, iron, or cobalt, and ZnO-Cu catalysts, respectively. Madon and Shaw (2) reviewed much of the early work dealing with effects of sulfur in Fischer-Tropsch synthesis. Only the most important conclusions of their review will be summarized here. 

In the forward synthesis, it turned out that the nitrile reduction was best done using hydrogen and a metal (Rh) catalyst. The final methylation of the primary amine had to be done via the imine and iminium ion (see Chapter 24) to prevent further unwanted alkylations. The reagent was an excess of formaldehyde (methanal CH2=0). Problem xx offers a chance to try this mechanism. 

CO2 reforming of methane (equation 1) has been proposed as one of the most promising technologies for utilization of these two greenhouse gases, and this synthesis gas is suitable for Fischer-Tropsch synthesis and oxygenated chemicals. A serious problem is carbon deposition via Boudouard reaction (equation 2) and/or methane decomposition (equation 3). 

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