To change the email account Word uses to send Mail Merges from in a Word document, you will have to make the email account you wish to send from temporarily the default in a couple of locations, before reverting to your usual default account.
Firstly in Outlook, click "File", then "Account Settings" and then on the sub-option for "Account Settings" again:
Highlight the account you wish to make the default and click "Set as Default". You will definitely need to set the default in the "Email tab" and you may also need to do it in the "Data Files" tab too:
After that, click "File" in Outlook again but this time click on the "Options" section:
Click on the "Mail" section on the left before scrolling down to the "Send Messages" area and ensuring that "Always use the default account when composing new messages" option is ticked: