Civ 5 runs through steam. Maybe someone hacked a program to run as a stand-alone, but technically, you need steam.
If I want to run without steam (to avoid the updates etc) I simply unplug my network cable and it will play in offline mode. I think it may be possible to set the game to run offline, but I never bothered to look for the settings.
You can start without steam window popping up but steam needs to run in the background. From inside steam right click on the game and there is option to create desktop shortcut which will open the game without needing to open the steam app directly.
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