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Open the file manager (by default PCManFM), go to /usr/share/applications. Right-click on the program you want to be added to your autostart programs, and click Copy. Now, go to ~/.config/autostart in PCManFM, right-click and click Paste. The program should be added to your autostart programs now, but double-check by clicking the LXMenu down left, click Settings, and then Desktop Session Settings.