My PC, on which I was using PSE 14, has totally died. Am I able to purchase the upgrade version of PSE 2022 for my new system which has no version of PSE installed?
Yes, you can purchase at the discounted upgrade price. But you may have to enter the old serial number as part of the installation procedure.
Sometimes you can find the non-upgrade license cheaper than the upgrade license if you look around.
Just make sure that it is from an authorized Adobe reseller: