梯度孔Hβ的制备及其催化苯加氢烷基化性能

Preparation of Hierarchical Porous Hβ and Its Catalytic Performance in Benzene Hydroalkylation

杨洋 孙娜 王雪 王钰佳 王海彦

Yang Yang Na Sun Xue Wang Yujia Wang Haiyan Wang

辽宁石油化工大学 石油化工学院，辽宁 抚顺 113001 中国石油化工股份有限公司 天津分公司，天津 300270

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China Sinopec Tianjin Petrochemical Company，Tianjin 300270，China

通过碱处理方法制备了具有不同结构和酸性的梯度孔Hβ分子筛，采用XRD、SEM、N2物理吸附和NH3?TPD表征方法对碱处理前后分子筛进行表征。以梯度孔Hβ分子筛为载体，采用等体积浸渍法制备Ru?Hβ双功能催化剂，并在固定床反应器上进行苯加氢烷基化反应活性以及稳定性评价。结果表明，经适量浓度碱处理后，提高了Hβ分子筛的介孔占比，有利于提高加氢烷基化活性以及稳定性。在氢气压力为2 MPa、反应温度为210 ℃、体积空速为1 h-1的条件下，Ru质量分数为0.2%时（以梯度孔Hβ分子筛质量为基准），与梯度孔Hβ组成的双功能催化剂可实现有效、稳定运行，苯的转化率达到54.32%，环己基苯选择性达到71.47%，催化剂稳定性在280 h内无明显下降。

Hierarchical porous Hβ molecular sieve with different structure and acidity were prepared by alkali treatment. XRD, SEM, N2 physical adsorption and NH3?TPD characterization methods were used to characterize molecular sieves before and after alkali treatment. With hierarchical porous Hβ molecular sieve as the carrier, the Ru?Hβ bifunctional catalysts were prepared by an equal volume impregnation method, and the benzene hydroalkylation reaction activity and stability were evaluated in a fixed bed reactor.The results show that Hβ molecular sieve can effectively increase the proportion of mesopores after being treated with a proper concentration of alkali, which is beneficial to improve the hydroalkylation activity and stability. At 2 MPa, 210 ℃ and a liquid hourly space velocity of 1 h-1, when the Ru mass fraction is 0.2% (based on the mass of hierarchical porous Hβ molecular sieve), the dual?functional catalyst composed of hierarchical porous Hβ can achieve effective and stable operation. At the same time, the conversion rate of benzene is 54.32%, the selectivity of cyclohexyl benzene is 71.47%, and the stability of the catalyst does not decrease significantly within 280 h.

辽宁省教育厅科研项目(L2019014)

10.3969/j.issn.1672-6952.2022.01.002