Sounds like thermostat , there should be cable with a pair of wires , one of the wires comes from timeclock when hw is switched on travels through the stat then the other comes out of stat down onto the brown wire of your zone valve, so check theres power coming back from stat through the brown wire, if there is then the stats fine, if not then its either up to temp or stat is gone . good luck
actually theres three stats as the immersion probably has one as well but not relevant to boiler firing i would bet on it being the overheat stat as its probably wired as a break in the orange wire hence your getting live in the junction box on orange