Wikipedia lists a few methane/LOX engines that have been used in test flights. For example, NASA's experimental Morpheus lander had fifteen or so test flights -- all low altitude, but some higher and longer lasting than StarHopper's hop today. It's also being developed simultaneously with Blue Origin's BE-4 engine, which hasn't flown yet, but has been through an extensive ground test program, and will be used on both Blue's own New Glenn orbital rocket and on ULA's Vulcan. So depending on how quickly the relevant test programs go, Raptor may or may not wind up being the first to be part of an orbital vehicle. (But as neither Vulcan nor New Glenn is currently slated to use it for the second stage, Raptor will very likely be the first to go all the way to orbit.)