Its difficult to give a reliable source for this, but searching in google it appears these words, for example in this page. But it's difficult to say this because there are lots of technical terms which are difficult to list, because many of them can be formed by adding a lot of prefixes.
Ciclopentanoperhidrofenantreno (30 letters) - Sterane
(31 letters in plural): Ciclopentanoperhidrofenantrenos
(wikipedia entry for it)
- Longest accepted word by RAE
Electroencefalografista (23 letters) - An expert in Electroencephalography
in plural it even has one letter more (24 letters) as electroencefalografistas