This is a problem solely between you and your wife. If you’ve made it clear that her friendship with her ex-brother in law bothers you, then it would be nice and appropriate if your feelings, as her husband, were more important than her feelings she gets from chatting up her ex-brother in law.
The question is what is it that you really want from your wife? You have to be clear in order to get something back from your wife. You’re not going to expunge this guy from your family’s life because he’s still living with your sister in law, and may even be the father of your nieces and nephews (if they have children together). So, even though he’s divorced from your sister in law, he’s still family. You’ll never completely get rid of this guy. If your wife calls her sister, there’s a good chance this guy will pick up the phone.
So ask your wife for something you can get. If you’d prefer she only talk to him when you’re in the room, then make that your request. If you’d prefer she not talk to him on the phone at all, then make that your request. If you prefer she not call him, or return his calls, but if he picks up when she calls her sister, she can make it short and sweet with him, then make that your request. If you prefer that she only talk to him on the phone when you talk to him first, then make that your request. If those things don’t work for you, figure out some way for you to request a boundary that she can give you.
So while you can’t eliminate him completely, your wife should be willing to make compromises with you to put your feelings first, and limit her contact with her ex brother in law.
Let me know if that helps. 🙂