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The composite powders composed of red mud (RM) and NH4H2PO4 (NH4H2PO4/RM) were successfully prepared by the anti-solvent method. The composition and structure of the NH4H2PO4/RM composite powders were characterized by the techniques of X-ray diffraction (XRD), SEM, N2 adsorption-desorption and Thermogravimetry-Differential scanning calorimetry (TG-DSC). The analysis results indicate that the as-prepared samples are composed with uniform nanoparticles and possess the porous structure. The methane explosion suppression characteristics of the NH4H2PO4/RM composite powders were tested by a 20 L spherical explosion system and a 5 L pipe test system. The results show that the NH4H2PO4/RM composite powders possess considerable suppression properties on methane explosion. When the loading content of NH4H2PO4 reached 30%, the maximum pressure and the maximum pressure rise rate of methane explosion were decreased by 35.1% and 95.8%, respectively. When comparing with no powder addition, the time to reach the pressure peak was extended from 0.07 s to 0.50 s. The NH4H2PO4/RM composite powders presented a synergistic suppression effect between NH4H2PO4 and RM, which made it exhibit considerable suppression property than that of pure NH4H2PO4 or red mud powders.