Do product and coproduct exist in the category of schemes? I only saw fiber product but didn't see product and coproduct of schemes, so do they not exist in general?
Actually, I am curious, in the definition of separated morphism/schemes, why we replace the product by fiber product?
You've asked three questions, so here are three answers.
First, for every scheme $X$, there is one and only one morphism of schemes $X \rightarrow \operatorname{Spec}\mathbb Z$. It follows that for two schemes $X$ and $Y$, the fiber product $X \times_{\operatorname{Spec} \mathbb Z} Y$ is the product of $X$ and $Y$ in the category of schemes.
Second, the coproduct $Z$ of any two schemes $X$ and $Y$ does exist in the category of schemes. Topologically, $Z$ is the disjoint union of $X$ and $Y$ with the disjoint union topology. If $W$ is open in $Z$, then the ring $\mathcal O_Z(W)$ is the product ring $\mathcal O_X(W \cap X) \times \mathcal O_Y(W \cap Y)$.
For the final question about why fibre product is used instead of product, I'll give an answer when your schemes are taken over a field $k$. One reason is that the fibre product over $k$ is a much nicer object than the product.
For example, suppose we consider the affine $k$-scheme $X = \operatorname{Spec} k[t]$. The fibre product is $X \times_{\operatorname{Spec} k} X$ is nothing more than $\operatorname{Spec}$ of the polynomial ring $k[x,y]$ in two variables. On the other hand, the product $X \times X$ is the spectrum of the horrible object $k[t] \otimes_{\mathbb Z} k[t]$.