No problem to spray paint vents, we do it all the time. The vents are not prone to any excessive heat in a forced air system, so any lacquer, acrylic or urethante paint will do the job. I have even coated wood grills with urethane. The existing powder coaing (most grills) will be adequate as a primer, just go straight to finish color. Be sure to completely clean and degrease the register before painting. I like to wipe with xylene or alcohol.
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