The “how” is something we may never know for sure, though the “when” is pretty set: the first artifacts of man-made glass come in the form of jewelry from ancient Egypt and Mesopotamia, and is dated from 3000-3500 years BC. back this far, the glass was not very transparent or refined.
The likely way that ancient cultures discovered the process is either by observing natural glass forming, when rocks melt and then re-solidify quickly from a volcano, lightning strike, etc., or it may have been a happy accident. According to the ancient Roman historian Pliny, the Phoenecians discovered glass when the nitrate blocks they were using to hold cooking pots melted and combined with the sand on the beach. This story is impossible to verify, but it puts the date for the start of glass-making back to around 5000 BC.
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