In order to explore the potential effects of abandoned coal mines on the water quality of Ordovician limestone aquifers, water-rock interaction simulations were conducted. After the closure of the coal mine, the karst water in the goaf area and the waste gangue had a geochemical reaction, and the above-mentioned water-rock process was simulated by an indoor static immersion experiment to explore the differences in the effect of different types of karst water on the dissolution of gangue. The basic water quality parameters pH, EC (electrical conductance), and ORP (oxidation-reduction potential) showed different trends in karst hydro-immersion solution and ultra-pure hydro-immersion solution; pH and EC had greater fluctuations in two sets of ultrapure hydro-immersion solutions, while ORP fluctuated more widely in three groups of karst hydro-immersion solutions. In addition, gangue minerals dissolved more significantly in bodies of water where limestone was added. The results of chemical component clustering showed that TDS (total dissolved solids) and EC were homopolymerized in each immersion solution, and subsequent correlation analysis showed that TDS and EC clusters were more significantly affected by mineral properties in ultrapure water-immersion solutions, and more affected by dominant ions in karst water-immersion solutions.