Patent GB-366494-A (GB)
Title: Improvements in the conversion of methane into liquid hydrocarbons
IPC: B01J19/02
Filed: 1930-09-22
Abstract: <PICT:0366494/III/1> <PICT:0366494/III/2> <PICT:0366494/III/3> The conversion of methane into hydrocarbons of higher molecular weight is effected in apparatus constructed at least in part of chromium, molybdenum, tungsten, or alloys of these metals with one another or of graphite.  The apparatus may be heated discontinuously in the manner of Cowper regenerators.  Any lustrous carbon deposited after long working may be removed mechanically or burnt off.  In examples (1) a gas containing 86,4 per cent of methane is passed through a graphite tube enclosed in a quartz or chamotte tube externally heated by an electric furnace to 1000-1020 DEG  C.; the exit gas contains 64,5 per cent of methane and 26,8 per cent of hydrogen, and the condensate boils below 110 DEG  C.; preferably the gas which has diffused into the space between the graphite and quartz tubes is sucked off from time to time, or this space may be filled with an inert gas at a higher pressure to minimize diffusion; (2) a gas containing 90 per cent of methane is passed at 1050 DEG  C. through an electrolytically chromed steel tube, a liquid product containing benzene and brown tar being obtained; similar results are obtained if the tube is chromed by diffusion of chromium powder by the action of heat or coated with an alloy of chromium and molybdenum for example by applying chromium electrolytically and then causing molybdenum to diffuse into the chromium layer; (3) and (4) a gas containing 95 per cent of methane is passed through a graphite tube A enclosed in a copper tube B, Fig. 1, filled with graphite pieces, or through a chamber B lined with graphite A and filled with graphite chequerwork C, C1, Figs. 2 and 3, at 1000 DEG  C.  The second Provisional Specification describes the use of graphite apparatus for other thermal conversions of hydrocarbons such as the conversion of olefines into higher gaseous olefines or liquid hydrocarbons and cracking substances of high molecular weight. The apparatus may be made of or lined with graphite and catalysts may be added.  In examples (1) a gas containing butylene, propylene, butane, propane, and ethane is passed through the graphite tube A, Fig. 1, at 850 DEG C.; (2) a gas containing 16,2 per cent of olefines obtained from cracking brown coal, is passed through the apparatus shown in Figs. 2 and 3 at 850 DEG  C.; (3) petroleum (b.p. 180-300 DEG  C.) is distilled through a graphite tube, Fig. 1, at 750 DEG  C.; the vapours are cooled to -80 DEG  C. and the condensate is allowed to attain room temperature, when it yields a gas containing 77 per cent of butylene, while the remaining liquid is a benzine, of b.p. 25-200 DEG  C.; the gas not initially liquefied contains 32,2 per cent of ethylene, 5,6 per cent of propylene and butylene, and 47,8 per cent of saturated hydrocarbons.  Reference has been directed by the Comptroller to Specifications 296,683 and 296,753, [both in Class 1 (i), Chemical processes &c.].ALSO:The conversion of methane into hydrocarbons of higher molecular weight is effected in apparatus constructed at least in part of chromium, <PICT:0366494/IV/1> <PICT:0366494/IV/2> <PICT:0366494/IV/3> molybdenum, tungsten, or alloys of these metals with one another or of graphite.  The apparatus may be heated discontinuously in the manner of Cowper regenerators.  Any lustrous carbon deposited after long working may be removed mechanically or burnt off.  In examples (I) a gas containing 86,4 per cent of methane is passed through a graphite tube enclosed in a quartz or chamotte tube externally heated by an electric furnace to 1000-1020 DEG  C.; the exit gas contains 64,5 per cent of methane and 26,8 per cent of hydrogen, and the condensate boils below 110 DEG  C.; preferably the gas which has diffused into the space between the graphite and quartz tubes is sucked off from time to time, or this space may be filled with an inert gas at a higher pressure to minimize diffusion; (2) a gas containing 90 per cent of methane is passed at 1050 DEG  C. through an electrolytically chromed steel tube, a liquid product containing benzene and brown tar being obtained; similar results are obtained if the tube is chromed by diffusion of chromium powder by the action of heat, or coated with an alloy of chromium and molybdenum, for example by applying chromium electrolytically and then causing molybdenum to diffuse into the chromium layer; (3) and (4) a gas containing 95 per cent of methane is passed through a graphite tube A enclosed in a copper tube B, Fig. 1, filled with graphite pieces, or through a chamber B lined with graphite A and filled with graphite chequer-work C, Cl, Figs. 2 and 3, at 1000 DEG  C.  The second Provisional Specification describes the use of graphite apparatus for other thermal conversions of hydrocarbons such as the conversion of olefines into higher gaseous olefines or liquid hydrocarbons and cracking substances of high molecular weight.  The apparatus may be made of or lined with graphite, and catalysts may be added.  In examples (1) a gas containing butylene, propylene, butane, propane, and ethane is passed through the graphite tube A, Fig. 1, at 850 DEG  C.; (2) a gas containing 16,2 per cent of olefines obtained from cracking brown coal, is passed through the apparatus shown in Figs. 2 and 3 at 850 DEG  C.; (3) petroleum (b.p. 180-300 DEG  C.) is distilled through a graphite tube, Fig. 1, at 750 DEG  C.; the vapours are cooled to -80 DEG  C. and the condensate is allowed to attain room temperature, when it yields a gas containing 77 per cent of butylene and propylene and 14,6 per cent of ethylene, while the remaining liquid is a benzine of b.p. 25-200 DEG  C.; the gas not initially liquefied contains 32,2 per cent of ethylene, 5,6 per cent of propylene and butylene and 47,8 per cent of saturated hydrocarbons.  Reference has been directed by the Comptroller to Specifications 296,683 and 296,753, [both in Class 2 (iii), Dyes &c.].