Yes you can do it. I dont know your specific boiler but the expansion vessel is behind the boiler and has a car valve type connector at the top. This is where you can connect a car tyre type pump/guage.
With zero pressure in the water system (front panel guage - you can probably let the pressure off by manually lifting/twisting the over pressure relief valve, or opening a bleed point on a radiator (v messy)) you will need 12 or 15 psi in the vessel (check your manual).
Before the pressure starts to build in the vessel you will need to displace around 8 litres of water (vessel specific)from the vessel through the over pressure vent or the bleed point, only then will the pressure start climbing, it takes a lot of pumping.
I do not know how reliable the expansion vessels are in your make, check that the vessel isnt faulty first by pushing down the central pin in the valve, if damp air with a little moisture comes out it is OK, if water squirts out it needs replacing, not recharging.
After recharging refill the system up to the top of the working pressure range, (1.5 bar?) turn the CH on and check that all is well. Recharging the vessel may also cure any need for frequent small water top ups.
While the system is at zero pressure it may be a good time to inject some fernox system protector maintanance gunk with a caulking gun at a bleed point, the adaptor supplied can be usefull when letting out the initial system pressure too. If you have any small leaks you could try giving it a shot of fernox leak sealing concentrate stuff as well.
An hour of fun for a wet Sunday afternoon.
c, May 2007