Use of unvented cylinder as a heat store?!

Yes probably true, but only in the UK do the locals actually bother enforcing them..
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If the P&T opens there is no fresh cold water to replenish/cool down the store. Thermal valves are available which you can connect to your DHW coil to cool the store - when it opens it allows mains water in which should then go to discharge. You will always need pressure protection - swap the P&T for a 3 bar relief which is standard on sealed CH.

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