3) The valves are "rated" for 450 F, but have soft seats which have melted and turned into glue, because
4) The asphalt has coked in the cavity of the valves, because the actual temperature the MI trace took the valves to is higher than you're admitting, or
5) The temperature inside the valves is lower than you think it is because you're measuring the temperature of the trace cables NOT the valve bodies much less the valve contents- and hence the asphalt is still a solid, glueing the valves shut
Just guesses here of course, because you haven't provided enough information for us to help further in a meaningful way aside from brainstorming crazy things that might be wrong here. Model numbers would help, as would specs.
A useless suggestion perhaps, but use gates next time! Unless they're actuated, why on earth you'd want the extra complexity and expense of a high temperature ball valve in this service is beyond me. You can't need better than class IV shutoff, and the gate valves will be a fraction of the price of ball valves which are actually suitable for that temperature. And as a bonus, when you try to open them, they'll likely actually open!