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Sorry was I being too obvious?

If you trace the flex from the cyl stat back to the wiring center and remove the lid from the wiring center. Be careful as there is mains voltage. I will guess that >the brown wire from the cyl stat will connect to the call from the prog. >the blue wire from the cyl stat will connect...

Not entirely sure I understand the OPs intention. I would move the cold storage cistern into loft, but leave cylinder where it is

Also check that the hot and cold are plumbed correctly

You need to confirm that you are getting a call from the programmer to the cyl stat by seeing if you have 240V on the cyl stat common. What cyl stat do you have? How is it wired?

It sounds like the cyl stat. Depending on how yours has been wired the valve should be:- >Grn / Yell Earth >Blue Neutral >Grey Perm Live >Brown Call from Cyl stat >Orangle S/L to boiler On your cyl stat...

I take it there was a hot water demand from the programmer and cylinder is not full of hot water

When the heating system is cold, run a hot tap - does the boiler fire up? If the boiler fires up - do you have hot water at tap? If you do not have hot water at tap - feel the flow pipe to the radiators where it leaves the boiler - is the flow pipe hot?

Does anyobe know if saniflo / grundfos type of condensate pumps can be used to take the PRV outlet from boilers? There specs say that they can handle 85deg for short periods. Thanks.

As long as it is not galvanised if I remember right.

When you say it fires up on DHW demand, but you get no hot water, how have you confirmed it is actually firing up?

Not quite sure if I understand your post correctly, but, the CO2 is often set per MI's then wound back 1% to give better overall burner efficiency over the year based on its efficiency / cleanliness dropping off as it reaches service time.