Thanks for the responses. I don't have any drills or taps long enough to go into the vee of the pulley, and don't really want to invest some if I can help it. The pulley I did indeed get at a tractor supply store. Is the key you showed in the image wedged shaped? I will not be reversing direction, and I can't used a collar because the shaft does not extend past the edge of the pulley. I only need to keep the pulley from working off the end of the shaft, even though the main force will be in the other direction (to keep it on, not off).
I will try to look for a gib head key, I guess.
Yes, they are wedge shaped, or to put it another way, they have a slight taper to them. They also work best in cases where there is a spacer sleeve on the shaft to keep the pulley a preset distance from the shaft bearing. This way when you drive the key in the pulley placement does not change. It can be a real challenge to get them right when the pulley is floating on the shaft! Of course, the other challenge is when you want to remove the key, especially if there is no room to work. They are really designed for speedy assembly such as in a factory and I've never seen a pulley designed for a gib head key as an aftermarket replacement, only as OEM parts. They are always cast iron or cast steel, never aluminum, and are not designed to be removed very often. If I had my choice when purchasing a pulley, if it is for anything other than fractional horsepower, I would purchase one that uses a split taper bushing such as Browning's QD series. Put them together with some anti-seize and you can get them apart whenever you need to.
Your best bet at finding a gib head key would be an implement dealer. I know for fact that they use a bunch of them on John Deere, Hesston, and CaseIH round balers (don't ask how I know!) but they are in the 5/16" and 3/8" sizes.
Removal is accomplished using a wedge that you drive in between the pulley hub and the head of the key. In most cases it is necessary to make the wedge to fit the specific application. You start by driving the wedge in with a hammer, keeping an eye out to make sure that the wedge does not start creeping up. Hammer it back down if necessary, then keep tapping and don't try hammering on the pulley as it will do you no good. After a bit, the key will begin to move slightly; keep going and you will soon see the key and the pulley coming apart from one another. Once it is loose you can pull the key out and slide the pulley off of the shaft.
One last thought: Did you by chance happen to purchase a pulley that missed a step in the manufacturing process, namely that of drilling and tapping for a setscrew? If that pulley is for a 3/4" shaft (you did say 3/16" key, right?) and it is a generic pulley purchased at TSC or a similar store, I would be willing to bet that it is supposed to have a set screw in it. Pulleys for gib head keys are almost non-existent in the generic parts world.