A chemical plant experienced a valve failure during a planned shutdown for maintenance that caused hydrogen to leak from a valve and catch fire. Four chemical reactor chambers in series were being emptied of liquid using hydrogen gas as part of a maintenance procedure. Two heater valves were opened allowing 3000 psi hydrogen to flow in reverse direction to purge the reactor system for approximately 25 minutes. At completion of the purging process, a "light" thud was heard as the reactor empty-out valves are being closed. Smoky vapor was observed coming out of one of the reactor empty-out valves and the valve closing was stopped by the operator. The operator summoned a second operator for help at which time a second "loud" thud was heard with a much larger light and view more