The steam reforming of hydrocarbons with special reference to methane

Abstract

From an examination of the literature relating to the catalytic steam reforming of hydrocarbons, it is concluded that the kinetics of high pressure reforming, particularly steam-methane reforming, has received relatively little attention. Therefore because of the increasing availability of natural gas in the U.K., this system was considered worthy of investigation. An examination of the thermodynamics relating to the equilibria of steam-hydrocarbon reforming is described. The reactions most likely to have influence over the process are established and from these a computer program was written to calculate equilibrium compositions. A means of presenting such data in a graphica1 form for ranges of the operating variables is given, and also an operating chart which may be used to quickly check feed ratios employed on a working naphtha reforming plant is presented. For the experimental kinetic study of the steam-methane system, cylindrical pellets of ICI 46-1 nickel catalyst were used in the form of a rod catalyst. The reactor was of the integral type and a description is given with the operating procedures and analytical method used. The experimental work was divided into two parts, qualitative and quantitative. In the qualitative study the various reaction steps are examined in order to establish which one is rate controlling. It is concluded that the effects of film diffusion resistance within the conditions employed are negligible. In the quantitative study it was found that at 250 psig and 6500C the steam-methane reaction is much slower than the CO shift reaction and is rate controlling. Two rate mechanisms and accompanying kinetic rate equations are derived, both of which represent 'chemical' steps in the reaction and are considered of equal merit. However the possibility of a dual control involving 'chemical' and pore diffusion resistances is also expressed.