I don't know about collector value but you can buy new all brass shotshells to load for about $1 each.
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David alot of the cowboy action guys use the brass shotgun hulls. And alot of them shoot BP in their loads. RCBS is even making a cowboy action set of dies for the all brass shell.
They do not have any real collectors value. But you should still be able to get $20 to $30 for them.
Do you belong to any forums that have some cowboy action shooters?? They would probably be interested in them. Tom.