The colours represented by hexadecimal values are based on RGB, rather than RYB. If you wanted blue, rather than using the complementary colour suggested by the traditional RYB wheel, orange, you would colour the flame particle texture yellow instead.
Colour changing works best with a black flame (or a white flame, if it's a "blend" flame). Any other colour, and there is no guarantee that you will be able to have the colour that you want. In addition, brightness functions as opacity, so it isn't possible to recolour a black flame into a white flame, as black on the particle texture would produce an invisible particle.