We know the familiar equivalent relation on $\mathbb{R}$, which is $$ x\sim y\Leftrightarrow x-y\in\mathbb{Q} $$
After quoting this relation, we have the quotient set $$ \mathbb{R}/_\sim = \{x + \mathbb{Q} : x\in\mathbb{R}\} $$
I know that if we want to construct a set of representative elements of the above relation, we need the Axiom of Choice. So if I write $$ \mathbb{R}/_\sim = \{[x] : x\in\mathbb{R}\text{ are representatives}\} $$
I need AC. But my question is, does existence of $\mathbb{R}/_\sim$ in the first formula need the axiom?
To my understanding, the existence of quotient set has nothing to do with the Axiom of Choice.
You don't need choice for the existence of $\mathbb{R}/{\sim}$, but you do need choice to assert that there is a set of $\sim$-class representatives.
To demonstrate this: we can say $$\mathbb{R}/{\sim} = \{ A \in \mathcal{P}(\mathbb{R}) \, :\, (\forall y,z \in A)(\forall q \in \mathbb{Q})(y-z \in \mathbb{Q} \wedge y+q \in A) \} \setminus \{ \varnothing \}$$ This can be proved to exist inside $\mathsf{ZF}$, because we can define $\mathbb{Q}, \mathbb{R}, \mathcal{P}(\mathbb{R}), +, -, \setminus, \varnothing$ in $\mathsf{ZF}$ and then apply Separation.
But a set of coset representatives is precisely (the image of) a choice function for $\mathbb{R}/{\sim}$, the existence of which does require the axiom of choice.