Welcome to the site
@ScottRPh .
Not entirely clear here. I can picture your wanting to install the first valve at the tank outlet.
This valve I can't picture unless it is right at the thru-hull ? What happened to the macerator pump in between ?
You may be able to empty the hose and subsequently fill with air if you close the first valve at the tank immediately after the macerator has pumped out all of the tank contents and start sucking air. However, you will still be stuck with a film of

inside the hose unless you can flush it with fresh water to clean it out. Without rinsing with fresh water, you haven't accomplished anything.
This is just way too much trouble and hassle to try to save this short length of hose when you can just plan on replacing it every 10 years or so at the same time you change the hose which leads from the head to the holding tank.
That 10 years before permeation is based on a top notch hose like Raritan/Saniflex Odor Shield Marine Hose or Trident Sani Shield Sanitation Hose.