[guided]Assume $R$ is closed in $X \times X$ and that $\pi$ is an open map. Let $[x], [y] \in X/{\sim}$ with $[x] \neq [y]$. Then $x \not\sim y$, so $(x, y) \notin R$. Since $R$ is closed, the complement $(X \times X) \setminus R$ is open, and by the definition of the product topology there exist open sets $U \ni x$, $V \ni y$ in $X$ with $U \times V \subset (X \times X) \setminus R$.
The condition $U \times V \subset (X \times X) \setminus R$ says: no element of $U$ is equivalent to any element of $V$. This immediately yields disjointness of the images: if $[z] \in \pi(U) \cap \pi(V)$, then $z \sim a$ for some $a \in U$ and $z \sim b$ for some $b \in V$. By transitivity, $a \sim b$, giving $(a, b) \in R$. But $(a, b) \in U \times V \subset (X \times X) \setminus R$, a contradiction. So $\pi(U) \cap \pi(V) = \varnothing$.
The key condition is openness of $\pi(U)$ and $\pi(V)$. By the definition of the quotient topology, $\pi(U)$ is open in $X/{\sim}$ if and only if $\pi^{-1}(\pi(U))$ is open in $X$. The set $\pi^{-1}(\pi(U))$ is the saturation of $U$ — the union of all equivalence classes that meet $U$. In general, the saturation of an open set need not be open (for example, if $X = \mathbb{R}$ with $0 \sim 1$ and $U = (-0.1, 0.1)$, then $\pi^{-1}(\pi(U)) = (-0.1, 0.1) \cup \{1\}$, which is not open). The hypothesis that $\pi$ is an open map is precisely the condition ensuring that the saturation of every open set is open.
Under this hypothesis, $\pi(U)$ and $\pi(V)$ are open, disjoint, and contain $[x]$ and $[y]$ respectively, establishing the Hausdorff property.
The condition that $\pi$ is open is equivalent to requiring that for every open $W \subset X$, the set $\{z \in X : z \sim w \text{ for some } w \in W\}$ is open. This holds automatically when equivalence classes are finite, when $X$ is a topological group and $\sim$ is defined by a closed normal subgroup, or more generally when the equivalence relation is "open" in the sense that the saturation map preserves open sets.[/guided]