Normal subgroups of $D_4$ are $N_1:=\text{Id}$, $N_2:=\langle r^2\rangle$, $N_3:=\langle r\rangle$, $N_4:=\langle r^2,s\rangle$, and $N_5:=D_2$. Let $n_k$, where $k\in\{1,2,3,4,5\}$, denote the number of group homomorphisms $\psi:D_4\to S_4$ such that $$\ker(\psi)=N_k\,.$$
Obviously, $n_5=1$ as the only group homomorphism $D_4\to S_4$ with kernel $N_5=D_4$ is the trivial homomorphism $x\mapsto 1_{S_4}$ for all $x\in D_4$. Now, $D_4/N_4\cong C_2$, where $C_r$ denote the cyclic group of order $2$. There are in total $$\binom{4}{2}+\frac{1}{2}\,\binom{4}{2}=9\text{ subgroups of }S_4\text{ isomorphic to }C_2\,.$$
Since $\big|\text{Aut}(C_2)\big|=\varphi(2)=1$, where $\varphi$ is Euler's totient function, we conclude that $n_4=1\cdot 9=9$.
Next, we again have $D_4/N_3\cong C_2$. As before, we obtain $n_3=9$. Now, $D_4/N_2\cong C_2\times C_2$. There are $$1+\frac{1}{2}\,\binom{4}{2}=4\text{ subgroups of }S_4\text{ isomorphic to }C_2\times C_2\,.$$
Since $\big|\text{Aut}(C_2\times C_2)\big|=(2^2-1)(2^2-2)=6$, we get $n_2=6\cdot 4=24$.
To calculate $n_1$, we must first count the number of subgroups of $S_4$ isomorphic to $D_4$. Since $|D_4|=8=2^3$ and $2^3$ is the largest power of $2$ that divides $|S_4|=4!=24$, we conclude that $D_4$ is a $2$-Sylow subgroup of $S_4$. The $2$-Sylow subgroups of $S_4$ are all conjugates. Since the only normal subgroups of $S_4$ are $\text{Id}$, $V$, $A_4$, and $S_4$ (where $V$ is isomorphic to the Klein $4$-group $C_2\times C_2$ and $A_4$ is the alternating group of order $\dfrac{4!}{2}=12$), and none of which is of order $8$, we see that $D_4$ is not a normal subgroup of $S_4$. Note that the intersection of two distinct $2$-Sylow subgroups of $S_4$ is exactly $V$. Since the number of $2$-Sylow subgroup is an odd number and we already know that this number is not $1$, and since $$|V|+j\,\big(|D_4|-|V|\big)=4+j\,(8-4)> 24-4=|S_4|-\Big|\big\{x\in S_4\,\big|\,x\text{ is of order 3}\big\}\Big|$$ for $j\geq 5$, we conclude that the number of $2$-Sylow subgroups in $S_4$ is precisely $3$. (Alternatively, the number $s$ of $2$-Sylow subgroups of $S_4$ is an odd number dividing $\dfrac{|S_4|}{2^3}=3$, and since $s>1$, we get $s=3$.) From this link, we know that $\big|\text{Aut}(D_4)\big|=4\cdot\varphi(4)=8$. Hence, $n_1=8\cdot 3=24$. For a list of all subgroups of $S_4$ isomorphic to $D_4$, see here.
In summary, the number of group homomorphisms from $D_4$ to $S_4$ is $$n_1+n_2+n_3+n_4+n_5=24+24+9+9+1=67\,.$$ In other words,
$$\big|\text{Hom}(D_4,S_4)\big|=67\,.$$