Blue light is scattered by aerosols. Red/orange colours are made visible.
Remember that sunlight is made up of different colors. When sunlight travels through this longer path in the atmosphere, blue light is scattered by more aerosols. By the time the light reaches our eyes, only colours such as red or orange are visible.
The shorter the wavelength, the more it is scattered.
Blue light is scattered because the shorter the wavelength, the more it is spread out by the atmosphere. Also, because aerosols are so small, they don't affect longer wavelengths as easily.