looking at your picture, I can see the 3-way valve, with the feed from the pump going into the bottom, and one of the exits going down through the floor, presumably to feed the rads, although it looks like it might be 28mm, which is odd. I can't see the pipe going into the bottom of the pump in the picture. Presumably there is one, and it goes to the boiler. Is the boiler downstairs from the cylinder?
the three-port valve seems to be at the top of a bunch of pipes. If it had air in it, how would the air escape? Is that the vent teed off just to the left on the cylinder feed?
the return from the bottom of the cylinder also looks odd. It appears to have a T from the F&E joining it from above; but then it seems to go two ways. One of them should go off to the boiler, but where does the other one come from? Is it the radiators return? Provided the gate-valve is open, any air at this point could escape up to the F&E, but it would tend not to have air in it because air would rise to the top of the coil. How would it escape from here?
what is that white-painted pipe beside the F&E wheel-head gate valve? Is it the cold feed to the cylinder? Or to the cold bath taps?
When the pump is running, does any water flow out of the vent into the F&E?