How would you reach the far side of the plate to insert the screws?
Using a screw from the opposite side as a stud is prone to fail because as you tighten the nut it may simply loosen the “stud”.
The proper way to secure a flanged joint in situations like this is by studs, preferably in blind holes, from the same side as their nuts. Proper studs that is, not bits of studding, so they enter only to the ends of their holding threads.
This seems a fundamentally weak detail-design, and the original builder may have had problems making the threads. Or had dis-assembled and re-assembled the superheater several times, damaging the threads in the purpose.
How thick is the flange and how well has it been silver-soldered to the tube-plate? If the structure is sufficiently sound it may be possible to drill right through and re-tap with a slightly larger and coarser thread. You need do some very careful measuring and thread-chart studying to establish the best.
Then use proper studs inserted with sealing-compound, using a stud-box to fit them. I would suggest stainless-steel studs with bronze nuts (or a different grade of stainless) with a touch of anti-seize compound to avoid galling.
The obvious snag is that the appropriate nuts won’t fit alongside that banjo-fitting – a spanner certainly won’t – so would need extended nuts and studs.