Another item
As a matter of safety, you cannot use allowable stress numbers alone as the final arbiter of safety. Note that the Code does this for approved materials -- but the fact that those bolts are approved means that they are sufficiently ductile, and their quality sufficiently controlled for use in pressure vessels.
For example, unless it's been changed recently, I don't believe that ASTM A325 structural bolts are suitable for pressure vessel flanges. You can also find very high strength aerospace fasteners that would easily meet strength requirements, but their lack of ductility would make them unsuitable for use.
I made this mistake once on the bonnet of a large valve using H900 condition 17-4 PH bolt to replace ones made from ASTM A193-Gr B7 ones. Mechanics were working on the valve while in service at 200 psi, removing one bolt at a time, replacing it with this higher strength bolt. The flange was about 6 foot in diameter as I recall. After installing about 20 bolts successfully, the head popped off a bolt being installed. A little while later, the same happened again. Had a progressive failure then resulted, we would have emptied the water from several miles of 12 foot diameter pipe in an around a strip mall. Perhaps a few of us would have survived.
Usually customers figure they can get a bolt of much higher strength and substitute it wily-nily just because the allowable stength exceeds the design limit. When I was stupider than I am today, I've followed this line of reasoning.
Just some advice -- stick with code approved fasteners and code compliant flange designs. Advise your clients that if they depart from this, they do so at their own peril. Maybe there's a legal loophole in the code somewhere that you could skirt legal responsibility, but there's two issues in play -- (1) code rules, and (2) intelligent action.