Hydrodeoxygenation of bio-oil model compounds over amorphous NiB/SiO2-Al2O3 catalyst in oil-water biphasic system
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摘要: 制备了负载型的非晶态NiB/SiO2-Al2O3催化剂，利用XRD、TEM、N2吸附-脱附和XPS表征手段对其进行了分析，并考查了催化剂在油水两相体系中对生物油模型化合物苯甲醚和愈创木酚的加氢脱氧性能。结果表明，在B的修饰作用下，Ni处于富电子状态，从而导致非晶态NiB/SiO2-Al2O3催化剂的加氢脱氧活性明显高于晶态Ni/SiO2-Al2O3催化剂。提高催化反应温度和延长反应时间有利于愈创木酚和苯甲醚的加氢脱氧转化。在实验结果的基础上，对愈创木酚和苯甲醚的加氢脱氧反应路径进行了分析，为生物油加氢脱氧反应机理提供了参考依据。Abstract: An amorphous NiB/SiO2-Al2O3 catalyst was prepared and characterized by XRD, TEM, N2 sorption and XPS. The catalytic performance of the prepared catalysts was evaluated in an oil-water bi-phase system using anisole and guaiacol as model compound of bio-oil. The results showed that Ni was in the electron-rich state with the modification of B, leading to the much higher hydrogenation activity of amorphous NiB/SiO2-Al2O3 catalyst than that of Ni/SiO2-Al2O3 catalyst. Increasing reaction temperature or prolonging reaction time was beneficial to the conversion of guaiacol and anisole. On the basis of the experimental results, the reaction pathway of guaiacol and anisole was analyzed, which provided a reference for the mechanism of bio oil hydrogenation.
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图 1 NiB/SiO2-Al2O3和Ni/SiO2-Al2O3催化剂的XRD谱图
Figure 1 Wide-angle XRD pattern of NiB/SiO2-Al2O3 and Ni/SiO2-Al2O3
图 2 催化剂NiB/SiO2-Al2O3 的氮气吸附-脱附等温曲线(a)和孔径分布(b)
Figure 2 N2 sorption isotherm (a) and pore size distribution curves (b) of NiB/SiO2-Al2O3
图 3 催化剂NiB/SiO2-Al2O3 中的Ni 2p和B 1s XPS谱图
Figure 3 XPS spectra for Ni 2p and B 1s of the NiB/SiO2-Al2O3 catalysts
图 4 催化剂NiB/SiO2-Al2O3(a)和Ni/SiO2-Al2O3(b)的透射电镜照片
Figure 4 TEM images of catalysts NiB/SiO2-Al2O3 (a) and Ni/SiO2-Al2O3(b)
图 6 催化剂NiB/SiO2-Al2O3和Ni/SiO2-Al2O3催化苯甲醚和愈创木酚加氢脱氧的活性对比
: cyclohexane; : cyclohexanol; : benzene; : cyclohexanone; : cyclohexene; : toluene; : methoxycyclohexane; : anisole; : phenol; ■: conversion
Figure 6 Anisole and guaiacol conversion and product selectivity over NiB/SiO2-Al2O3 and Ni/SiO2-Al2O3 (reaction time: 3 h, p: 5 MPa, t: 260 ℃)
图 7 反应温度对NiB/SiO2-Al2O3催化苯甲醚(a)和愈创木酚(b)转化率和产物选择性的影响
(a): : cyclohexane; : cyclohexanone; : methoxycyclohexane; : cyclohexanol; : cyclohexene; —■—: conversion; : benzene; : toluene (b): : cyclohexanol; : cyclohexane; : toluene; : cyclohexanone; : phenol; : anisole; : cyclohexene; : benzene; —◆—: conversion
Figure 7 Anisole (a) and guaiacol (b) conversion and product selectivity over NiB/SiO2-Al2O3 at different temperature (reaction time: 3 h, p: 5 MPa)
图 8 反应时间对NiB/SiO2-Al2O3催化苯甲醚(a)和愈创木酚(b)转化率和产物选择性的影响
(a): : cyclohexane; : cyclohexanol; : benzene; : cyclohexanone; : methoxycyclohexane; —◆—: conversion; : cyclohexene; : toluene (b): —◆—: conversion；: cyclohexanone; : anisole; : phenol; : toluene; : cyclohexene; : cyclohexane; : cyclohexanol; : benzene
Figure 8 Anisole (a) and guaiacol (b) conversion and product selectivity over NiB/SiO2-Al2O3 for different reaction time (t: 260 ℃, p: 5 MPa)
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