Stan, you can flame harden with oxy acetylene using a carburising flame but the skin is very thin, a few microns. Set the flame to oxygen week I.e. With a long centre cone, this means the carbon fuel gas is not being fully consumed thus an excess of carbon in the flame, heat the part and keep at bright cherry red for a while, several mins, then quench in water. Might work with oxy propane but never tried this . The surface will be toughened rather than glass hard but nevertheless more wear resistant.
Not a very efficient way to harden and as I said the surface is VERY thin, best way is as Nobby says to case harden with Kasnit or similar.
I know nothing of steam valves but if you want them hardened why not make them of a suitable hardening steel, EN8 or EN9 the latter hardens easier and harder but you will need to temper them as well.
Regards John