ok if i got your right, you have blp's and want them bigger?
PNG should support transparency but i don't know for sure.
I always use .tga to make changes to any wc3 texture and then convert it
back to .blp with BLP lab. Also be sure that when saving any texture in BLP lab,
when clicking the 'Alpha Channel' button in the saving window, the 'leave alpha
channel without changes' is used, or the alpha channel might be lost (or 'add
alpha channel sould your source texture be without one).
Also to make changes to .tga files you need some sort of program like PS, or
GIMP (freeware, i use it). Paint does not support .tga or at least does not save
their alpha channel.