Deactivation mechanism of Cu/SiO2 catalyst in gas phase hydrogenation of furfural to furfuryl alcohol
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摘要: 采用共沉淀法制备了Cu/SiO2催化剂，在固定床反应器上评价其糠醛气相催化加氢制备糠醇的反应性能，并采用XRD、H2-TPR、ICP-OES、XPS、TG、Raman、TEM等手段对使用后的Cu/SiO2催化剂进行表征，研究其在反应中的失活机理。在常压、反应温度140 ℃、质量空速2.4 h−1、氢醛比9.7的条件下，反应5 h内糠醛转化率均高于97%；反应6−21 h，糠醛转化率从96%快速下降到32%，说明Cu/SiO2催化剂在糠醛加氢反应中快速失活，失活的主要原因是活性组分铜的团聚烧结和催化剂表面上积炭覆盖了反应活性位。
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关键词:
- 共沉淀法 /
- Cu/SiO2催化剂 /
- 糠醛加氢 /
- 失活机理 /
- 糠醇
Abstract: The Cu/SiO2 catalysts were prepared by co-precipitation and tested for hydrogenation of furfural to furfuryl alcohol in a fixed bed reactor. The deactivation mechanism of the catalysts was investigated by characterization of H2-TPR, ICP-OES, XPS, TG, Raman and TEM. Under the conditions of atmospheric pressure, reaction temperature of 140 ℃, mass space velocity of 2.4 h−1 and the molar ratio of hydrogen to furfural of 9.7, the furfural conversion was higher than 97% in the first 5 h. However, the conversion of furfural decreased rapidly from 96% to 32% after 21 h of reaction, indicating that Cu/SiO2 catalyst was rapidly deactivated. The factors for the deactivation of Cu/SiO2 catalyst were the agglomeration and sintering of the active component copper. Moreover, the carbon deposition on the catalyst surface resulted in the covered active site Cu0. -
图 1 不同催化剂上(a)糠醛的转化率和(b)糠醇的选择性
Figure 1 Conversion of furfural (a) and the selectivity of furfuryl alcohol (b) over the catalysts Reaction conditions: t=140 ℃, p=0.1 MPa, H2/FUR=9.7, WHSV=2.4 h−1
图 3 还原和使用后催化剂的TEM和HRTEM图像
Figure 3 TEM and HRTEM images of the reduced and used catalysts
图 4 催化剂的(a)N2吸附-脱附等温线和(b)孔径分布
Figure 4 N2 adsorption-desorption isotherms (a) and pore size distribution (b) of catalysts
图 6 焙烧、还原和使用后催化剂的Cu 2p XPS谱图
Figure 6 XPS spectra in the Cu 2p region of the calcined, reduced and used catalysts
图 7 还原和使用后催化剂的Cu LMM俄歇谱图
Figure 7 Cu LMM Auger spectra of the reduced and used catalysts
图 8 还原和使用后催化剂的TEM图像和催化剂中Cu、Si、C分布的元素映射
Figure 8 TEM images and elemental mapping images of the reduced and used catalysts (a): 40Cu/SiO2-0; (b): 40Cu/SiO2-5; (c): 40Cu/SiO2-13; (d): 40Cu/SiO2-21
图 9 (a)催化剂的拉曼光谱谱图；(b)催化剂的拉曼光谱分峰拟合；(c)催化剂的C 1s XPS谱图；(d)催化剂的TG曲线
Figure 9 (a) Raman spectra; (b) Raman spectral peak splitting fitting; (c) C 1s XPS spectra and(d) TG curves of the catalysts
表 1 Cu/SiO2催化剂的物理化学性质
Table 1 Physicochemical properties of the Cu/SiO2 catalysts
Catalyst Cu loadinga
w /%Cu loadingb
w /%Weight lossc
w /%SBETd /
(m2·g−1)vtotald/
(cm3·g−1)dpored /nm TEM /nm Reduction
peak areae40Cu/SiO2 – – – 184 0.52 11.4 – 2210.4 40Cu/SiO2-0 30.7 – – – – – 12.3 – 40Cu/SiO2-5 29.2 30.6 5.8 142 0.45 11.1 14.1 476.3 40Cu/SiO2-13 28.6 30.4 7.5 153 0.47 13.6 17.9 369.4 40Cu/SiO2-21 26.9 30.9 11.4 139 0.45 15.6 19.8 336.6 a: copper content of the used catalysts is calculated by ICP-OES; b: copper content of the used catalysts after calcination is calculated by ICP-OES; c: detected by TG; d: determined by nitrogen adsorption; e: detected by H2-TPR 
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表 2 催化剂表面不同铜物种占比
Table 2 Percentage of different surface copper species
Catalysts BE /eV KE /eV x(Cu + ) /%a Cu 2p3/2 Cu + Cu0 Cu + / (Cu + + Cu0) 40Cu/SiO2 933.7 – – – 40Cu/SiO2-0 932.5 916.2 918.3 22.6 40Cu/SiO2-5 932.2 916.4 918.5 26.2 40Cu/SiO2-13 932.3 916.6 918.7 28.1 40Cu/SiO2-21 932.5 916.7 918.9 29.8 a Ratio of Cu + to (Cu + + Cu0) obtained by deconvolution of Cu LMM spectra
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表 3 40Cu/SiO2-21催化剂的C 1s XPS分析
Table 3 XPS analysis of C 1s XPS of 40Cu/SiO2-21 catalyst
Binding energy /eV Chemical state of carbon Quantity /% 284.2 graphitized carbon 24.0 285.2 amorphous carbon 52.7 286.6 alcohol C–OH or C–O bond 16.7 288.1 carbonyl 6.6
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