WO3对Pt/α-Al2O3催化萘深度加氢的促进作用

doi:10.11949/0438-1157.20211030

摘要/Abstract

摘要：

采用无酸性的α-Al₂O₃为载体，预先沉积WO₃然后浸渍法负载Pt物种，合成了系列Pt-WO₃/α-Al₂O₃催化剂用于萘深度加氢反应，系统地研究了氧化钨物种在萘加氢反应中的作用。通过XRD、Raman、HRTEM、XPS和H₂-TPR技术表征了Pt和WO₃物种在载体表面的分散情况和状态，并利用Py-IR研究了载体负载氧化钨和Pt前后的酸性质变化。在温和的反应条件下（70℃、3 MPa、1 h）Pt-WO₃/α-Al₂O₃催化剂表现出优异的萘深度加氢活性，萘的转化率和十氢萘的选择性均达到100%。结果表明，预先在载体表面引入的WO₃和Pt产生了强相互作用，WO₃提高了Pt物种的分散程度，催化剂的酸性来源于氧化钨物种的引入且和负载量成正比关系。催化剂较强的酸性和较高的Pt分散程度是Pt-WO₃/α-Al₂O₃在低温条件下能够使萘深度加氢的关键因素，对于十氢萘作为储氢介质工艺具有重要的意义。

关键词: 萘, 十氢萘, 载体, 氧化钨, 加氢, 催化剂

Abstract:

Pt-WO₃/α-Al₂O₃ catalysts were prepared with sequential impregnation of WO₃ and then Pt in α-Al₂O₃ supports without acid sites. The as-prepared were investigated the promotion of WO₃ catalysts in the reaction of hydrogenation of naphthene at mild reaction conditions. XRD, Raman, HRTEM, XPS, and H₂-TPR analyses reveal the basic structure and distribution of Pt and WO₃ species. Py-IR analyses reveal that the changing of acid sites after loading Pt and WO₃ species. Pt-WO₃/α-Al₂O₃ catalysts have shown excellent catalytic performance for the hydrogenation of naphthalene to decalin at mild reaction conditions (70℃, 3 MPa, 1 h) with the conversion and selectivity of decalin are 100%. Combined with the characterization and catalytic performance, the pre-introduced Pt and WO₃ species caused the strong interaction between Pd sites and WO₃ and the efficient distribution of Pt by WO₃ species. The strong acidity of the catalyst and the high degree of Pt dispersion are the key factors for the deep hydrogenation of naphthalene by Pt-WO₃/α-Al₂O₃ under low temperature conditions, which is of great significance for the process of decalin as a hydrogen storage medium.

Key words: naphthalene, decalin, support, tungsten oxide, hydrogenation, catalyst

中图分类号:

O 643.36

梁瑜, 赵彤, 赵斌彬, 刘雷, 董晋湘, 唐明兴, 李学宽. WO₃对Pt/α-Al₂O₃催化萘深度加氢的促进作用[J]. 化工学报, 2021, 72(11): 5643-5652.

Yu LIANG, Tong ZHAO, Binbin ZHAO, Lei LIU, Jinxiang DONG, Mingxing TANG, Xuekuan LI. Promotion of WO₃ species on Pt/α-Al₂O₃ for the deep hydrogenation of naphthalene[J]. CIESC Journal, 2021, 72(11): 5643-5652.

图/表 11

图1 粉末XRD衍射谱图

Fig.1 Powder XRD patterns of samples

图2 样品的Raman谱图

Fig.2 Raman spectra of samples

图3 催化剂HRTEM图

Fig.3 HRTEM images of catalysts

图4 α-Al2O3负载WO3、Pt前后样品的H2-TPR曲线

Fig.4 H2-TPR profiles of α-Al2O3, 20%WO3/α-Al2O3 and 1%Pt-20%WO3/α-Al2O3 samples

图5 催化剂的Pt 4f、W 4f XPS和XPS全谱分析

Fig.5 XPS spectra of Pt 4f and W 4f of catalysts

图6 1%Pt-xWO3/α-Al2O3的Py-IR光谱

Fig.6 Py-IR spectra of 1%Pt- xWO3/α-Al2O3 catalysts

图7 萘在1%Pt-xWO3/α-Al2O3催化剂上加氢反应结果(反应条件：0.05 mol/L萘溶液5 ml，催化剂0.02 g，初始H2压力3 MPa，反应温度70℃，时间1 h)

Fig.7 The reaction results for naphthalene hydrogenation over 1%Pt-xWO3/α-Al2O3 catalyst (reaction conditions: 5 ml naphthalene solution of 0.05 mol/L, 0.02 g catalyst, 3 MPa initial H2 pressure, temperature of 70℃, and time of 1 h)

图8 yPt-20%WO3/α-Al2O3催化剂上萘加氢反应结果(反应条件：0.05 mol/L萘溶液5 ml，催化剂0.02 g，初始H2压力3 MPa，温度70℃，时间1 h)

Fig. 8 The reaction results for naphthalene hydrogenation over yPt-20%WO3/α-Al2O3 catalyst (reaction conditions: 5 ml naphthalene solution of 0.05 mol/L, 0.02 g catalyst, 3 MPa initial H2 pressure, temperature of 70℃, and time of 1 h)

图9 1%Pt-20%WO3/α-Al2O3催化剂在不同反应温度下萘加氢的反应结果(反应条件：0.05 mol/L萘溶液5 ml，催化剂0.02 g，初始H2压力3 MPa，时间1 h)

Fig.9 Catalytic results for naphthalene hydrogenation over 1%Pt-20%WO3/α-Al2O3 at various reaction temperature (reaction conditions: 5 ml naphthalene solution of 0.05 mol/L, 0.02 g catalyst, 3 MPa initial H2 pressure, and time of 1 h)

图10 1%Pt-20%WO3/α-Al2O3催化剂4次循环使用反应结果(反应条件：0.05 mol/L萘溶液5 ml，催化剂0.02 g，初始H2压力3 MPa，时间1 h)

Fig.10 Reusability of the 1%Pt-20%WO3/α-Al2O3 catalyst for naphthalene hydrogenation (reaction conditions: 5 ml naphthalene solution of 0.05 mol/L, 0.02 g catalyst, 3 MPa initial H2 pressure, and time of 1 h)

图11 第一次反应后1%Pt-20%WO3/α-Al2O3催化剂XPS谱图

Fig.11 XPS spectra of Pt 4f and W 4f for 1%Pt-20%WO3/α-Al2O3-Used catalysts

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WO₃对Pt/α-Al₂O₃催化萘深度加氢的促进作用

Promotion of WO₃ species on Pt/α-Al₂O₃ for the deep hydrogenation of naphthalene

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