级孔Pt-Ni/ZSM-5对木质素衍生物加氢脱氧性能研究

doi:10.11949/0438-1157.20210192

摘要/Abstract

摘要：

利用等体积共浸渍法制备了级孔ZSM-5分子筛负载Pt-Ni双金属催化剂，并系统研究了不同Pt/Ni比对愈创木酚和二苯并呋喃二元混合物加氢脱氧反应性能的影响。采用XRD、N₂-BET、SEM、TEM和H₂-TPR对Pt-Ni催化剂的形貌和结构进行了表征。Ni掺入量较少时（1%和3%，质量分数），有利于促进活性金属的分散，增强Pt-Ni双金属之间的协同作用；当Ni掺入量增加到5%时，活性金属出现较严重的团聚。二元混合物加氢脱氧实验结果表明与单金属Pt/HZ-75相比，双金属Pt-Ni/ZSM-5催化剂均表现出优异的加氢脱氧催化活性，Ni的引入显著提高了反应转化速率，并提高了产物中联环己烷的选择性。随着Pt/Ni比的降低，Pt-Ni催化剂的活性逐渐增加，而联环己烷选择性先升高后降低。Pt-3Ni/HZ-75催化剂在3 MPa、260℃下表现出最佳的催化活性和联环己烷选择性，反应4 h后转化率达到100%，联环己烷选择性达到43%。

关键词: 催化, 二元混合物, 分子筛, 木质素, 加氢脱氧, 级孔ZSM-5, 双金属

Abstract:

The Pt-Ni bimetallic catalyst supported on the graded pore ZSM-5 zeolite was prepared by the equal volume co-impregnation method, and the effect of different Pt/Ni ratios on hydrodeoxygenation performance of guaiacol and dibenzofuran was systematically studied. The physicochemical properties of the as-synthesized Pt-Ni catalysts were characterized via XRD, N₂-BET, SEM, TEM and H₂-TPR. The results showed that when the loading amount of Ni was small (1% and 3%,mass ratio), it was beneficial to promote the dispersion of active metals and enhance synergistic effect between Pt-Ni bimetals. However, the active metals would agglomerate with the increase of Ni loading to 5%(mass). Compared with the Pt/HZ-75 catalyst, all the Pt-Ni/ZSM-5 catalysts exhibited excellent hydrodeoxygenation catalytic activity, and the introduction of Ni significantly improved the conversion rate and enhanced the selectivity to bicyclohexane. Furthermore, with the decrease of Pt/Ni ratio in Pt-Ni/ZSM-5 catalyst, the catalytic activity of Pt-Ni catalysts gradually increased, while the selectivity to bicyclohexane first increased and then decreased. The Pt-3Ni/HZ-75 catalyst showed the best catalytic activity and bicyclohexane selectivity at 3 MPa and 260℃. After 4 h of reaction, the conversion rate reached 100% and the bicyclohexane selectivity reached 43%.

Key words: catalysis, binary mixture, moleclar sieves, lignin, hydrodeoxygenation, hierarchical ZSM-5, bimetal

中图分类号:

TQ 032.4

李晓雪, 牛晓坡, 王庆法. 级孔Pt-Ni/ZSM-5对木质素衍生物加氢脱氧性能研究[J]. 化工学报, 2021, 72(5): 2626-2637.

LI Xiaoxue, NIU Xiaopo, WANG Qingfa. Study on hydrodeoxygenation performance of hierarchical Pt-Ni/ZSM-5 for lignin derivatives[J]. CIESC Journal, 2021, 72(5): 2626-2637.

图/表 9

图1 不同催化剂的扫描电镜图

Fig.1 SEM images of different catalysts

图2 不同催化剂的N2吸附-脱附等温线和BJH孔径分布

Fig.2 N2-adsorbtion-desorption isotherms and pore size distributions of different catalysts

表1 不同催化剂的比表面积和孔结构性质

Table 1 Specific surface area and pore structure properties of different catalysts

催化剂	S_BET/(m²/g)	S_meso/ext/(m²/g)	V_total/(cm³/g)
Pt-Ni/HZ-75	522.1	365.2	0.3254
Pt-3Ni/HZ-75	511.6	345.1	0.3048
Pt-5Ni/HZ-75	508.5	309.9	0.2655

图3 不同催化剂的X射线衍射图

Fig.3 XRD patterns of different catalysts

图4 不同催化剂的高倍透射电镜和粒径分布

Fig.4 HR-TEM images and particle size distribution histograms of different catalysts

图5 不同催化剂的HAADF-STEM和元素Mapping图

Fig.5 HAADF-STEM and Mapping images of different catalysts

图6 不同催化剂的H2-TPR谱图

Fig.6 H2-TPR curves of different catalysts

图7 不同催化剂下二元化合物的转化率和产物选择性

Fig.7 Conversion and products selectivity of binary compound over different catalysts

图8 不同Pt/Ni比催化剂下二元化合物的转化率和产物选择性

Fig.8 Conversion and products selectivity of binary compound over different catalysts

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