That is a questionable modification. If the materials used in the original construction are capable of withstanding the higher temps, that might be possible. I experimented with secondary combustion in an old wood stove that I had modified into a sandbox heat sink with copper tubing in the sand to capture the heat and send to emitters.
In this case secondary air inlets were directed into a chambered stove-top flue. The sandbox was around and above this secondary combustion area. It worked great at secondary combustion and achieved temps above 1400 F. However, and this is important, the sheet steel construction of the stove could not tolerate the high temps and fatigued to a dangerous level quite rapidly.
I would think the engineers who worked on the design of your boiler did not plan it as a gasification boiler or it would be one. It sounds very risky to attempt something likes this inside your home. The possible loss of structure, loved ones, and loss of insurance coverage due to your modifications is nothing to take lightly.