http://www.nexusmods.com/skyrim/mods/39143/ is a bit like Kragenir's in that it gives NPCs some extra topics based on their location and/or profession. (http://static-3.nexusmods.com/15/mods/110/images/39143-2-1375156156.jpg)
http://www.nexusmods.com/skyrim/mods/36099/ gives several of the follower NPCs a bit more dialogue--some of it is romance-focused, but some is based on location and such. (http://static-2.nexusmods.com/15/mods/110/images/36099-1-1368689469.jpg)
My own mods, http://www.nexusmods.com/skyrim/mods/22650 (http://static-4.nexusmods.com/15/mods/110/images/22650-1-1356890770.jpg) and http://www.nexusmods.com/skyrim/mods/11450 (http://static-1.nexusmods.com/15/mods/110/images/11450-1-1365280460.jpg) give the members of the Companions guild some extra lore- and character-friendly unique dialogue.
All of the above rely on silent dialogue because of the difficulties matching new dialogue to the existing voices. The excellent http://www.nexusmods.com/skyrim/mods/8429/ mod gets around this issue of voices by adding a large number of new NPCs with unique dialogue, voiced by a large collection of the community's best voice actors. It's not quite what you're after in terms of expanding the vanilla game's NPCs, but it's definitely worth a look if you enjoy exploring characters in an RPG as much as exploring dungeons. (http://static-4.nexusmods.com/15/mods/110/images/8429-2-1349322121.jpg)