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With Civ 3 Vanilla you can´t have 31 civs. If I remember well, here the maximum is 16 civs.
With Civ 3 PTW or Civ 3 Conquests you can have a maximum of 31 Civs + the Barbarians. In that case you must add the addidional civs to the scenario and enlarge the the number of civs in the scenario properties to 31.
There are tutorials for adding civs and units. You can look at the stickied thread in this forum about the modmaker tutorial or at the more modern tutorials at Civfanatics.
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