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There is a petrol station on the highway you can access with a bus.Take bus 2 direction Saint-Sylvain-D'Anjou and leave at Parc des expositions. Just behind the roundabout there is a petrol station you can access (it's also possible to hitch at the roundabout).
This spot didn't work for me because it is still in the city so cars don't really want to stop. I think it would be better that try to take another bus go further in direction Cholet, bring a board written Cholet, once you reach Cholet, try to find a gas station or air de repose, it would be easier to hitch to other cities.