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In this study, tri-butyl-phosphate (TBP)-kerosene is used as the extraction solvent to remove phenols from coal gasification wastewater, and the complex mechanism of the extraction is investigated. An effect experiment is conducted to determine the complex structures, the enthalpy change of reaction, and the effect of extraction solvent concentration and temperature on the distribution coefficient. To predict the extraction effect before the experiment, the distribution coefficient mathematical model of phenol extraction is established, which is based on a liquid-liquid extraction model and verified for accuracy by the experiment. The effect experiment result shows that with an increase in concentration of TBP and decrease in temperature, the extraction distribution coefficient increases and further determines the complex structures and the enthalpy change of the reaction. Meanwhile, a comparison of experimental and calculated values in the model experiment result shows that the average relative error of extraction distribution coefficient is 5.56% in different concentrations of TBP and 2.72% in different temperatures. Considering the error of the experiment, this work concludes that the distribution coefficient mathematical model of phenol extraction has a high predictive effect on the distribution coefficient and extraction rate of volatile phenol in actual wastewater. [ABSTRACT FROM AUTHOR]