Beauty and charm quarks are ideal probes of pertubative Quantum Chromodymanics in proton–proton collisions, owing to their large masses. In this paper the role of multi-parton interactions in the production of doubly-heavy hadrons is studied using simulation samples generated with Pythia , a Monte Carlo event generator. Comparisons are made to the stand-alone generators BcVegPy and GenXicc . New methods of speeding up Pythia simulations for events containing heavy quarks are described, enabling the production of large samples with multiple heavy-quark pairs. We show that significantly higher production rates of doubly-heavy hadrons are predicted in models that allow heavy quarks originating from different parton–parton interactions (within the same hadron–hadron collision) to combine to form such hadrons. Quantitative predictions are sensitive to the modelling of colour reconnections. We suggest a set of experimental measurements capable of differentiating these additional contributions.