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Just to avoid any confusion, you cannot upgrade 32-bit Windows to 64-bit. You need to do a fresh install, so back up any data and settings before you commence. Windows Easy Transfer is a simple way to do this. Note that you cannot transfer programs, so you will need the original disks and keys to reinstall them.
The key provided with the retail version of Windows 7 works for both 32- and 64-bit versions. It is just possible that you might need to call the Microsoft activation number to activate the new copy of Windows, though I have never had to do this when transferring Windows 7 to a new machine (but not a 32-64 move). Obviously you will need to stop using the 32-bit install.
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