The biggest concern with the refrigerator on propane heat when travelling is that there is now an exterior open flame, a real hazard at a fuel stop with gasoline vapors floating around. And, yes, the ammonia/hydrogen refrigerant itself is flammable. The modern propane refrigerators have a meltable thermal link in series with the 12 volt controller power. This meltable fuse is located near the flame/boiler and designed to cut off the 12 volt DC power in the event of a fire. Cutting off the 12 volt DC power cuts off the electrically energized propane inlet valve removing this possible fuel from a fire.
I also bought a self deploying halon fire extinguisher which I have mounted in the external refrigerator compartment.
Most all of our big 5th wheel RV's are towed by diesel trucks. Diesel fuel does not have many vapors, as compared to gasoline. Otto Diesel's first engine ran on vegetable oil.
I leave the refrigerator on "Automatic" mode when travelling. That way it is on AC when plugged to shore power, and on propane when travelling. I fuel up the truck unhitched from the trailer each day. This eliminates the fuel vapor hazard. Also, many owners have had collisions with posts, awnings, etc. at gas stations when trying to maneuver a big hitched up 5th wheel rig around the gas station.
I had some problems with the 12 volt DC line to the refrigerator blowing its fuse, due to an intermittent wire short. I was towing in 100 degree plus weather from Oregon to Sacramento. I saw my refrigerator heat up on the road during those days.