Bhapps, how about letting us know what you did and what was found. Chrome plated brass valves don't normally seize in the tank neck since they are removed so often during routine inspections. Long ago, I saw some Navy aluminum tanks with that problem but they had beryllium copper valves which had been in place for years.
When replacing the valve, a bit of silicone, Christolube or Krytox on the threads would be a reasonable precaution. I wouldn't use anything else due to odor or toxicity. Silicone shouldn't be used if the tank is to be charged with oxygen (as in partial pressure mixing).
Most valves have a machined flat for wrenching. The tank should be secured in a chain vise. Use newspaper to protect the metal from gouging.