Sounds like something is happening then. Something is getting into the cylinders. In my experience it takes at least a couple of complete purge cycles to get a good steady supply of fuel at the injectors so you might want to run it a few more times. If the battery voltage is 12.2v with everything off, what is it when the engine is turning over? TD5s are very fussy about getting a high voltage when the starter motor is turning too. If it drops into single figures it's unlikely that the engine will catch.
The other possibility is some problem of compatibility between the new ECU and the engine, and Discovery versus Defender, as this guy had http://www.web-rover.co.uk/my_td5.html?n=3
While cranking battery was reading around 10 volts going down to 8+ volts.