4-杂氧庚二醇是丙二醇生产过程中的杂质，通过催化水解反应可水解生成1，3-丙二醇，提高丙二醇收率。采用等体积浸渍法制备磷改性的ZSM-5分子筛，作为水解催化剂。通过X射线衍射、³¹P固体核磁和X射线光电子能谱等表征手段分别对催化剂样品的结构、酸性及磷在分子筛上的存在形态等进行表征；通过评价研究磷改性对其催化水解性能的影响。结果表明：磷改性显著降低ZSM-5分子筛的酸密度，且强酸中心和弱酸中心的变化趋势不同；随着磷含量的增加，磷与骨架铝的作用逐渐增强，当磷含量提高到4%（质量分数，下同）以上时，磷酸盐的聚合度增加明显；而ZSM-5分子筛表面P₂O₅物种占比随磷负载量增加呈现先升高后降低的趋势。随着ZSM-5分子筛中磷含量的增加，4-杂氧庚二醇的转化率提高，而丙二醇的选择性则先升高后降低；磷负载量为2%~4%时能得到最优的水解性能，且磷负载后提高ZSM-5分子筛4-杂氧庚二醇水解稳定性。

4-hexoheptanediol is an impurity in the production process of propylene glycol.It can be hydrolyzed to 1，3-propanediol through a catalytic hydrolysis reaction，thereby increasing the yield of propylene glycol.A phosphorus-modified ZSM-5 zeolite was prepared as a hydrolysis catalyst using the equal volume impregnation method.The structure，acidity，and the form of phosphorus in the zeolite of the catalyst samples were characterized by X-ray diffraction，³¹P solid-state NMR，and X-ray photoelectron spectroscopy respectively.The effect of phosphorus modification on its catalytic hydrolysis performance was studied through evaluation.The results showed that phosphorus modification significantly reduced the acid density of the ZSM-5 zeolite，and the trends of change for strong acid centers and weak acid centers were different.As the phosphorus content increased，the interaction between phosphorus and framework aluminum was gradually strengthened.When the phosphorus content was increased to more than 4%（mas fraction，the same below），the degree of phosphate polymerization was increased significantly.The proportion of P₂O₅ species on the surface of the ZSM-5 zeolite was firstly increased and then decreased with the increase in phosphorus loading.With the increase in phosphorus content in the ZSM-5 zeolite，the conversion rate of 4-hexoheptanediol was increased，while the selectivity of propylene glycol was firstly increased and then decreased.The optimal hydrolysis performance was achieved when the phosphorus loading was between 2% and 4%，and the phosphorus loading improved the hydrolysis stability of 4-hexoheptanediol on the ZSM-5 zeolite.