Just to add my experiences over the last few days here in the NE where daytime temperatures have been stuggling to get to 0C (nightime is down to -5C). Central Heating boiler comes on at 0820 and went off at 1030 this morning (no overnight heating in the house) - the room where the thermostat is (my lounge) was a toasty 13C when I got up. So 2 hours later the lounge is now at 17C and my better half used the shower as well. Total usage so far today has been 18.25kWh. During the day the thermostat will be left at 17C. Judging by recent previous days I will be using between 45 and 50 kWh of gas but the house will be a fairly constant temperature going between 16.5C and 17.5C and will go on/off when it gets lower/higher than these respective temperatures. I'm not sure that turning the thermostat up for these 2 periods is going to save anything as the thermostat temperature might not be reached anyway.
In addition to turning off the eco/comfort setting on your boiler another thing you could try doing is to reduce the boiler flow temperature a little (especially if yours is set at 70+C) to see how that affects your has usage. Many now have it set on 60C and some even lower (mine is set at 50C) - the radiators still get hot (or they should do) but maybe not scauldy hot. With the Domestic Hot water temperature setting, again you can turn it down a little - hot enough to run a bath and/or hot enough to draw a bowl of hot water to do dishes - mine is set at 55C and is perfectly adequate for my needs. Depending on how well insulated your property is, using your boiler in a slightly different way may save you more £££ and avoid excessively low temps during the day.
Yesterday saw me use 48.59kWh at a cost of £5.22 and the house reasonably comfortable from about 10am-10pm although, to be clear, I'm not on a prepayment meter so am on a different tariff.