Effective treatment of coal slime water is essential for sustainable coal preparation plant operation but hindered by the stable suspension of fine, negatively charged particles. To address this, a novel star-shaped inorganic–organic hybrid polymer (aluminum hydroxide-polyacrylamide, Al-PAM) was synthesized via in situ polymerization. Its performance was systematically compared with well-established coagulants/flocculants—polyaluminum chloride (PAC), non-ionic polyacrylamide (NPAM), and their binary combination through settling tests and quartz crystal microbalance with dissipation monitoring (QCM-D). The results showed a positive correlation between the molecular weight of Al-PAM and its flocculation efficiency. The optimal variant, Al-PAM-442, achieved an exceptionally high initial settling rate (50.4 m/h) and low supernatant turbidity (45.77 NTU) at an ultralow dosage of 6 mg/L. QCM-D analysis elucidated the mechanism: Al-PAM forms a thick, soft, and irreversibly adsorbed hydrated layer on silica, enabling strong electrostatic anchoring and effective polymer bridging. In contrast, PAC adsorption was reversible, while NPAM formed a thin, compact film with poor bridging capacity. Although the combined PAC/NPAM system showed synergistic performance, it required a significantly higher dosage (70 mg/L). This study demonstrates that the star-shaped Al-PAM architecture successfully integrates charge neutralization and bridging into a single molecule, offering a highly efficient and practical solution for industrial coal slurry dewatering.

High-ash coal slime water, characterized by its stable colloidal suspension of fine kaolinite particles, poses a significant challenge in the coal preparation industry because it is hard to achieve efficient solid–liquid separation. While traditional coagulants and flocculants often suffer from limited bridging capabilities and distinct pH sensitivity, novel molecular architectures offer potential solutions. In this study, a star-shaped inorganic–organic hybrid flocculant (Al-PAM) was synthesized via in situ polymerization. Its flocculation performance and interfacial adsorption mechanism on the specifically targeted aluminol basal plane of kaolinite were systematically investigated and compared with Polyaluminum Chloride (PAC), Non-ionic Polyacrylamide (NPAM), and their combination (PAC + NPAM). Settling tests revealed that Al-PAM exhibited superior performance at a significantly lower dosage (10 mg∙L⁻¹) compared to the PAC + NPAM binary reagent system. It achieved a rapid initial settling velocity and reduced the supernatant turbidity to 48.45 NTU, while maintaining a near-neutral pH favorable for water recycling. Furthermore, Quartz Crystal Microbalance with Dissipation (QCM-D) monitoring confirmed that Al-PAM forms a thick, viscoelastic, and irreversible adsorption layer on the Al₂O₃ substrate. The dissipation shifts (ΔD) revealed that the star-shaped architecture promotes distinct bridging and electrostatic adsorption, overcoming the limitation of linear polymers. This work elucidates the specific contribution of the alumina-surface interaction with flocculants and proposes an efficient strategy for treating refractory coal slime water.