Very often, this is a gasket problem. Use the thinnest gasket material that is properly rated for the service. Go back after the line has been up to temperature for about 24 hours and re-torque the bolts. Very often, you don't get anything on them, but sometimes I've seen nuts loose enough that they're not even finger tight.
I've also seen problems at flanges due to thermal expansion and contraction of the line. This is not the flanges themselves expanding, but the line itself moving, and "cocking" the flange, resulting in a gasket leak that showed up every time the line cooled off and contracted. Once the anchor for the expansion joint was repaired, the problem went away.