Lots of possibilities here. Is your PNG really actually a semi-Transparent one? Load it into a Photo Editor and export it as JPG, it will no longer have transparency. Then upload your new JPG version to Roll20. Did you put it on the GM Layer? It will seem transparent if it's on GM layer but will turn Opaque if you move to Token layer, or move to Map Layer and "Move to Front". Alternatively you can easily obscure a section of your Map, using the Roll20 drawing tools. This is the fast easy way to make an opaque shape of any size. Alternatively again you can use Fog Of War, Roll20 feature, to opaquely obscure any part of your Map BUT it will be transparent for the GM-Only.