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Without knowing where you live, and more specifically the number of degree-days of heat you need, it’s hard to say. A typical standard efficiency boiler will have an AFUE of about 80% when set up and maintained properly. A high efficiency unit (condensing) will be in the low 90’s. All things being equal, you might save 100 gallons a year. It might not be economical to replace a unit that still has lots of life left in it if payback is your only concern.
One thing that is worth looking into is the replacement of the electronics and motor on any burner that is more than a few years old. Pre/post purge primary controls will allow the burner to stay cleaner longer and interrupted ignition (which turns off the spark once the flame is lit) will save electricity and cut electrode wear significantly. If you dont change the control, at least replace the ignition transformer with an electronic ignitor. The newer capacitor type motors run alot cooler and use less current.
I’d concentrate first on making sure that your home is well insulated, including windows and doors, and making sure that you don’t have excessive air infiltration.
Don