How do you clean a cast iron black fireplace?
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http://homeguides.sfgate.com/restore-cast-iron-fireplaces-20521.html
I love cast iron fireplaces! Its definitely going to require elbow grease and steel wool! Good luck!
Are you going to use it again? If so, I'd go to a reliable hardware/big box facility and talk with an experienced sales person. There are products that you can safely paint cast iron stoves with. Products that can withstand heat. Anything less and you might find a smoke screen when you build your next fire. Do a search on the internet "cast iron paint"/"paint for cast iron stoves".
Have the stack cleaned out, start a long, fire for many days. I used a sos pad and scrub it. I would not paint it until it is very clean, otherwise it just builds up.
Steel wool is your best option!