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Invariably there will be plumbing problems. If you find yourself with a copper plumbing fitting that needs to be removed get ready to apply the heat. That is, the heat of a torch. For the most part, the only reason to un-sweat or un-solder a fitting is that you have a leak and it needs to be replaced, or maybe you are re-routing some plumbing lines.
You first will want to have a little wiggle room at the pipe-to-fitting connection. This connection will need enough room to be pulled apart once the joint is loosened, so plan on a few inches anyway. You may have to loosen pipe straps or hangars to get clearance. Also, since you will be working with a torch, have a bucket of water nearby in case you catch nearby lumber on fire. It's a good idea to use a flame cloth and cover any flammable material you will be working near (like wood studs or joists).
Drain the piping so that the pipes can get hot enough to melt the solder. If there is water in the piping, you will turn it into steam and it won't get hot enough to allow you to disassemble the parts. Once you are ready, light the torch and apply the tip of the cone to the fitting just inside of the edge. Keep the flame moving slightly around the perimeter of the fitting to uniformly heat it up. While you are doing this, use large channel locks to slowly pull apart the fitting and the pipe. You will find that heat travels quickly. I recommend using large channel locks or water pump pliers not because you will need a lot of leverage, but because the heat from the pipe well travel quickly and you will feel it in your hand. Once you have the pipe and fitting separated, let everything cool before you start working with them again. Here is some information on how to solder copper pipe.
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