The 10—20qkeV Ar16+ and Ar17+ ions produced by SECRAL enter on metallic surface of Zr. In this interaction，the multi-electron excitation possibly occurred in the neutralization of the highly charged Ar16+ ions，which produced vacancy in the K shell. Electron of the high n state de-excited to K vacancy gives off X-ray. The experimental results show that X-ray intensities for the Ar hollow atom decrease with increase of incidence energy，and Lβ X-ray intensities of target atom Zr increase with increasing incidence energy. Kα X-ray yield per ion for Ar17+ was five orders of magnitude greater than that for Ar16+.