Who last put that valve on? You or a shop? If a shop did, and you still have the receipt, I'd take it back to them and ask them to show you how to take it off...
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Drop it off for a VIP
Fill the tank, then open the valve wide open to cool the metal (metal shrinks when frozen) then unscrew it while it's still cold.
Drop it off for a VIP
When installing a valve in an aluminum cylinder ALWAYS use Dow Corning 111 to prevent seizing and galling. You can actually tear the threads out of an aluminum cylinder by using brute force.
Tank vise and a good long pipe wrench. Heat the tank neck with a heat gun. The valve will be shredded but it will come off or break, one way or the other you will want a new valve.
Someone suggested heating the tank with a heat gun. That's fine as long as you recognize the tank will also be scrap. Any portion of the tank heated over about 325 degrees F will lose its heat treatment and be too soft to safely hold air.