Based on the definition of a small category $\mathcal{C}$ being a category whose objects form a set, coudln't we define a graph $G=(V,E)$ and an operation $\cdot:E\times E\to E$ where $(x,y)\cdot (y,z)=(x,z)$, $V=\text{Ob}(\mathcal{C})$ and $(x,y)\in E\iff \exists f\in\text{Hom}(\mathcal{C})\ \text{s.t.}\ f:x\longrightarrow y$? Because $G$ is reflexive, we have $(x,x)\in E$ or, what it's same, $\exists f\in\text{Hom}(\mathcal{C})\ \text{s.t.}\ f:x\longrightarrow x$; and because of transitivity, we know that if $(x,y)$ and $(y,z)$ are in $E$, then $(x,z)$ is in $E$, so $\exists f,g,h\in\text{Hom}(\mathcal{C})\ \text{s.t.}\ f:x\longrightarrow y\land g:y\longrightarrow z\land h:x\longrightarrow z$, meaning that the identity and associative laws do seem to hold in $\mathcal{C}$.
Couldn't we define a small category as a transitive reflexive graph together with an associative operation?
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Yes, something along these lines does indeed hold: a category is a directed graph (possibly with parallel arrows, i.e. allowing more arrows $a\to b$ for points $a,b$) equipped with an associative composition operation on its paths, including paths of length 0, i.e. objects - giving the identity arrows.
A directed graph can be given by a pair of sets $V,E$ and a pair of functions $source,\ target:E\to V$.
(In categorical context these are called the domain and codomain of a morphism (=arrow)).
We can generalize it to get a version of directed 'bipartite graph': a span (in $Set$) from set $A$ to set $B$ is a pair of functions with common domain, $(s:E\to A,\ t:E\to B)$.
We can still regard elements of $E$ as arrows, $s$ as source and $t$ as target, and then all arrows of a span go from a point of $A$ to a point of $B$.
If for every $a\in A$ and $b\in B$ there is at most one arrow between them, then we get back the notion of binary relation between $A$ and $B$.
Now, spans $A\leadsto B$ and $B\leadsto C$ can be composed in a natural way (well, only up to isomorphism and just almost associatively), and we can also define morphisms between spans.
So, a directed graph is just an 'endo-'span $G:V\leadsto V$. The arrows of the span composition $GG$ are the paths in $G$ of length 2 (the composable pairs of arrows), and thus giving a composition will be just a span morphism $GG\to G$. We can also formulate the associativity and unit constraints.
All in all:
Sets and spans make a bicategory, in which
- the endomorphisms are the directed graphs,
- and the internal monoids are exactly the categories!
What you've written seems to only allow for at most one morphism between objects. Now, if you alter it to fix this situation, giving:
then you do indeed capture the notion of a category. But note that the presence of multiple morphisms with the same source/target means that the structure provided by composition is in general extremely complicated, so it really is misleading (in my opinion) to think of a category as "just a graph with a bit of extra stuff."