Yes, you can use Methylated spirits to remove the leftover traces of silicone sealant. To remove the bulk of the sealant though you want to use a Stanley Knife or sharp chisel.
So Methylated Spirits will remove silicone but only the remnants. To remove the bulk of the silicone you want to use something really sharp. A Stanley knife, scalpel, chisel or even a specialist tool are all good choices.
You want to break the seal at the top and bottom of the silicone. You should then be able to peel the silicone away. Try and go slow to stop the silicone from snapping, this way you will remove most of the material in one go.
It is after doing this that you will undoubtedly be left with bits of silicone all over. These left-behind parts are what you can use Methylated Spirits to remove.
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You can dab some Methylated spirit onto the silicone leftovers. leave it for a few minutes to hopefully soften up the silicone a little.
You can then try and rub the silicone off with a rag, reapplying the spirits to the rag whenever needed.
There are also specialist silicone softening products like the one below that you can purchase.
When it comes time to put down some nice new silicone you want to be particularly sure the methylated spirits have properly dried.
If not they may stop the new silicone from properly sticking. Meaning it may just peel off!
Luckily Methylated spirits evaporate really quickly and do not leave much residue behind. This is why they are so prized as a cleaner for pretty much everything.