One common factor across many economies around the world is their high dependency on petroleum. The chemical sector is no exception and considering the paramount role that solvents play within this industry they make an ideal focus for investigating green transition potential. This work attempts to shed some light on the scarce literature regarding the quantitative assessment of substitution capacity in target markets, by examining a case study of toluene use as an industrial cleaning agent and its replacement by limonene, a widely established citrus‐peel‐derived alternative in a number of applications. The systematic approach presented here compares market demand against potential supply by evaluating current and projected scenarios based on citrus fruit and juice production both at global and regional level. The results clearly show that the potential for complete substitution of toluene by limonene at global level is certainly out of reach, but encouraging results were obtained in specific regional substitution case studies, considering both citrus‐producing and citrus‐importing countries. In these cases, there is a clear potential for limonene to substitute toluene as a solvent within and beyond the cleaning sector, leaving space for future work in this area to investigate the transition potential for other important bio‐based chemicals. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd