If I understand the question correctly, you are intending to send the data bits directly over the power line, without any modulation. That gonna be problematic.
Particularly, you are considering an AC coupling of RS485 data. But the standard RS485 bus signal can't be AC coupled, because it's not a DC balanced signal, it has a dedicated idle level, and the duty cycle of character frames varies between 10 and 90%. Even more problematic, you can't couple an AC signal to the power lines without decoupling the low impedance DC path for AC, e.g. by chokes. Transformers are another option. Possibly, the signal drivers must be considerably stronger than standard RS485. The feasibility of a solution depends also on the current rating of the DC supply.
In any case a kind of modulation or encoding of the original serial data stream to form a DC balanced signal would be needed.