I thought the higher the KW rating then the quicker it would get to temperature, however it seems this isn't necessarily efficient.
Sort of but not really and its definitely not efficient. There is only so much heat the boiler can put into the loop based on the amount of water in it, the flow rate, the effectiveness of the heat exchanger and how quickly the rads can get rid of the heat into the house. For a boiler to heat the house at 35kw, you need rads capable of getting rid of 35kw.
If you have a regular routine (e.g. you are out at work for the same 10 hours daily) then you are usually better off using set back temperatures rather than letting the hose cool down fully and then heat back up again because of how efficient the boiler is during its different modes. If its running fill tilt, its considerably less efficient than if its tricking in heat to keep the house at a cooler but above ambient (~16C) temperature and then heating the house up the few degrease to get it back to ~20C.
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