中空Pt/ZSM-5催化剂用于愈创木酚加氢脱氧合成环烷烃

doi:10.11949/0438-1157.20210191

摘要/Abstract

摘要：

采用溶解-重结晶方法合成了不同硅铝比具有级孔壳的中空ZSM-5分子筛，并对其负载Pt催化剂（Pt/HZ-x）催化愈创木酚加氢脱氧制备环烷烃性能进行了探究。通过X射线晶体衍射（XRD）、场发射扫描电子显微镜（SEM）、场发射透射电子显微镜（TEM）、氮气吸附脱附（N₂-BET）、氨气程序升温脱附（NH₃-TPD）和X射线光电子能谱（XPS）对合成的系列催化剂进行了物化性质表征。得益于特殊的中空级孔结构，中空ZSM-5分子筛具有高外比表面积和介孔孔容，有利于促进活性金属Pt的分散和增强反应物的传质。Pt/HZ-x催化剂表现出了优异的催化性能和愈创木酚加氢脱氧活性，在220℃的低温即可以达到100%的环烷烃选择性。另外，随着分子筛载体酸性的减弱，愈创木酚加氢脱氧产物的二次反应程度降低，增大了环己烷的选择性。

关键词: 中空分子筛, 生物燃料, 催化, 愈创木酚, 加氢脱氧, 合成, 环烷烃

Abstract:

Hollow ZSM-5 zeolites with different Si/Al molar ratios and hierarchical porous shell were fabricated via employing dissolution-recrystallization strategy, and utilized as support to load precious Pt (Pt/HZ-x) for hydrodeoxygenation of guaiacol to cycloalkanes. The physicochemical properties of the as-synthesized catalysts were characterized by powder X-ray crystalline diffraction (XRD), field emission scanning electron microscope (SEM), field emission transmission electron microscope (TEM), nitrogen adsorption and desorption (N₂-BET), ammonia temperature program desorption (NH₃-TPD) and X-ray photoelectron energy spectroscopy (XPS). Benefit from the special hollow structure, hollow ZSM-5 zeolites exhibited a larger external specific surface area and mesoporous volume, which was favorable to promote the dispersion of metallic Pt and mass transfer of reactants. The Pt/HZ-x catalysts showed excellent catalytic performance and hydrodeoxygenation activity for guaiacol, and could reach 100% selectivity to cycloalkanes at a low temperature of 220℃. In addition, as the acidity of the molecular sieve carrier weakens, the degree of secondary reaction of the guaiacol hydrodeoxygenation product decreases, which increased the selectivity to cyclohexane.

Key words: hollow zeolite, biofuel, catalysis, guaiacol, hydrodeoxygenation, synthesis, cycloalkanes

中图分类号:

TQ 032.4

牛晓坡, 徐爽, 李晓雪, 冯富祥, 王庆法. 中空Pt/ZSM-5催化剂用于愈创木酚加氢脱氧合成环烷烃[J]. 化工学报, 2021, 72(5): 2616-2625.

NIU Xiaopo, XU Shuang, LI Xiaoxue, FENG Fuxiang, WANG Qingfa. Hollow Pt/ZSM-5 catalysts for highly selective hydrodeoxygenation of guaiacol to cycloalkanes[J]. CIESC Journal, 2021, 72(5): 2616-2625.

图/表 11

图1 中空ZSM-5分子筛的制备示意图

Fig.1 Schematic representation of the preparation process of hollow ZSM-5 zeolite

图2 不同中空ZSM-5分子筛的SEM(左)和TEM（右）图

Fig.2 SEM and TEM images of different hollow ZSM-5 zeolites

图3 不同中空ZSM-5分子筛的X射线衍射图

Fig.3 XRD patterns of different hollow ZSM-5 zeolites

图4 不同中空ZSM-5分子筛的N2吸附和脱附等温曲线和BJH孔径分布

Fig.4 N2 adsorption and desorption isotherms and the corresponding BJH pore size distributions of different hollow ZSM-5 zeolites

表1 不同中空ZSM-5分子筛的比表面积和孔结构性质

Table 1 Specific surface area and pore structure properties of different hollow ZSM-5 zeolites

样品	比表面积/(m²/g)			孔容/(cm³/g)
样品	S_BET	S_micro	S_ext	V_total	V_micro	V_ext
HZ-100	383.51	192.89	190.61	0.2656	0.0937	0.1719
HZ-200	386.96	186.79	200.17	0.2585	0.0804	0.1781
HZ-300	385.46	204.82	180.64	0.2662	0.0964	0.1698

图5 不同中空Pt/ZSM-5催化剂的NH3-TPD图

Fig.5 NH3-TPD profiles of Pt/HZ-100, Pt/HZ-200 and Pt/HZ-300 catalysts

表2 不同中空分子筛负载Pt催化剂NH3-TPD定量数据

Table 2 Acidity properties of Pt/HZ-100, Pt/HZ-200 and Pt/HZ-300 catalysts

样品	峰温/℃			酸量/(μmol/g)
样品	Peak Ⅰ	Peak Ⅱ	Peak Ⅲ	Weak	Midium	Strong	Total
Pt/HZ-100	188	315	401	274.30	59.25	167.15	500.71
Pt/HZ-200	177	285	380	128.37	43.80	87.75	259.93
Pt/HZ-300	152	206	307	77.83	22.29	70.16	170.27

图6 不同中空Pt/ZSM-5催化剂的XPS图

Fig.6 XPS spectra of Pt/HZ-100, Pt/HZ-200 and Pt/HZ-300 catalysts

图7 不同中空Pt/ZSM-5催化剂上愈创木酚随温度变化的转化率

Fig.7 Conversion of guaiacol as a function of temperature over Pt/HZ-100, Pt/HZ-200 and Pt/HZ-300 catalysts

图8 不同中空Pt/ZSM-5催化剂催化愈创木酚加氢脱氧产物选择性

Fig.8 Product selectivity as a function of temperature over Pt/HZ-100, Pt/HZ-200 and Pt/HZ-300 catalysts

图9 不同Pt/HZ-x催化剂在280℃时环己烷和二次反应产物的选择性数据

Fig.9 Cyclohexane and secondary reaction selectivity at 280℃ over different Pt/HZ-x catalysts

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