Objective Although increasing the amount of inert hydrophobic material can improve the anti-caking performance of compound fertilizer, carrying inert hydrophobic material hinders the applicability of compound fertilizer in mechanized fertilization and the integrated technology of water and fertilizer. In order to reduce the amount of inert hydrophobic material applied to the outer surface of the compound fertilizer particles, in this article, the type and proportion of nitrogen salt, phosphorus salt, and potassium salt were limited so as to increase the anti-caking performance of the particles. Methods The anti-caking performance of 17-17-17SOP nitro-compound fertilizer granules (AN-NPK) was modified by the following three measures: (1) APP (ammonium polyphosphate) was used to replace some inorganic phosphates; (2) reducing the mass fraction of AN (ammonium nitrate) and introducing KN (potassium nitrate) to supplement the nitrate nitrogen in the compound fertilizer, and maintain the same ratio of nitrate nitrogen and ammonium nitrogen in AN-NPK; (3) reduce the mass fraction of KS (potassium sulfate), and shift the molar ratio of NO3/SO4 away from 2.0. The AN modified by APP and KN was characterized by X-ray diffraction and differential scanning calorimetry. The mechanism of improving the anti-caking performance of AN-NPK was demonstrated. Results The results showed that when the mass fraction of APP in the formula was 0%, 8%, 16%, and 21%, the anti-caking performance of AN-NPK is gradually increased, the transverse shear force of the agglomerates decreased from 135.65 N to 94.02, 67.45, and 60.32 N. When 10% KN and 12% APP were added to AN-NPK, the transverse shear force continued to decrease to 33.25 N. Conclusion The mechanism of improving anti-caking performance of AN-NPK is as follows:(1) APP with oligomeric degree has higher solubility and mobility than monoammonium phosphate and diammonium phosphate, resulting in higher enrichment on the surface of AN-NPK; (2) at the granulation temperature of 80 °C, KN releases more potassium ions than KS, and more AN was modified in the granulation process of AN-NPK. In summary, APP combined with KN weakens the phase transition effect of AN and reduces the salt ion concentration on the surface of AN-NPK.
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