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Steam Reforming Processes. (see also Gas Production, Chap. 2).

. As the nickel-containing catalysts are sensitive to poisons, any sulfur compounds present in the hydrocarbon feedstock have to be removed by hydrodesulfurization, generally with a combination of cobalt molybdenum and zinc oxide catalysts [430 432]. Adsorption on activated carbon is an alternative when the feed is natural gas with a rather low sulfur content. RSH+H2RH+H2S (23) H2S+ZnOZnS+H2O (24) The general overall reaction can be formulated as CnH(2n+2)+n H2O_nCO+(2n+1)H2 (25) or more specifically for methane, usually the major constituent of natural gas, as: CH4+H2O_CO+3 H2 H = +206 kJ/mol (26) To introduce nitrogen to achieve the required stoichiometric hydrogen/nitrogen ratio for ammonia synthesis, STEAM REFORMING REACTION The reforming reaction is split into two sections. In the first section, the primary reformer, the reaction proceeds in indirectly heated tubes filled with nickel-containing reforming catalyst and is controlled to achieve a partial conversion only [in conventional plants 65% based on methane feed, leaving around 14 mol% methane (dry basis) in the effluent gas]. In the following secondary reformer A refractory-lined vessel filled with nickel catalyst the gas is mixed with a controlled amount of air introduced through a nozzle (burner). By combustion of a quantity of the gas the temperature is raised sufficiently (to about 1200 C) that the endothermic reforming reaction is completed with the gas adiabatically passing the catalyst layer. In this way the outlet temperature is lowered to around 1000 C, and a residual methane content of 0.5% or lower (dry basis) is attained in conventional plants [100, 418]. Nitrogen already present in the natural gas tends to

cause a reduced specific air ratio in the secondary reformer and a reduced secondary reformer temperature rise. Therefore, to maintain the same methane leak, the primary reformer exit temperature must be increased.