糠醛气相加氢制备糠醇Cu/SiO<sub>2</sub>催化剂的失活机理研究

于冬冬; 于欣瑞; 张雅静; 王康军

doi:10.1016/S1872-5813(23)60362-7

糠醛气相加氢制备糠醇Cu/SiO₂催化剂的失活机理研究

doi: 10.1016/S1872-5813(23)60362-7

于冬冬^1,,
于欣瑞^1,,
张雅静^1, ,,
王康军^1, ,

沈阳化工大学化学工程学院, 辽宁沈阳 110142

基金项目: 辽宁省高等学校创新人才支持计划（辽教函[2020]389号），辽宁省兴辽英才计划（XLYC1907029）和沈阳市中青年科技创新人才支持计划（RC210365）资助

详细信息

作者简介:
于冬冬(1992年生)，男，硕士研究生

通讯作者:
Tel: 024-89383902, E-mail: yjzhang2009@163.com

angle_79@163.com

中图分类号: TQ426.8
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- 被引次数: 0
出版历程
- 收稿日期: 2023-03-06
- 修回日期: 2023-04-10
- 录用日期: 2023-04-17
- 网络出版日期: 2023-05-06

Deactivation mechanism of Cu/SiO₂ catalyst in gas phase hydrogenation of furfural to furfuryl alcohol

YU Dong-dong^1
,,
YU Xin-rui^1
,,
ZHANG Ya-jing^{1
, ,},
WANG Kang-jun^{1
, ,}

College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China

Funds: The project was supported by Liaoning Innovation Talents Program in University (Liao[2020]389), Liaoning Revitalization Talents Program (XLYC1907029) and Shenyang Young and Middle-aged Science & Technology Talents Program (RC210365)

摘要

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。
- 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 were 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.
- co-precipitation /
- Cu/SiO₂ catalyst /
- hydrogenation of furfural /
- deactivation mechanism /
- furfuryl alcohol

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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

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图 2 焙烧后催化剂的XRD谱图

Figure 2 XRD patterns of calcined catalysts

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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

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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

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图 5 催化剂的H₂-TPR图

Figure 5 H₂-TPR profiles of the catalysts

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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

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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

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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

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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 1_S XPS spectra and(d) TG curves of the catalysts

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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 loading^a w /%	Cu loading^b w /%	Weight loss^c w /%	S_BET / (m²·g⁻¹)^d	v_total/ (cm³·g⁻¹)^d	d_pore /nm^d	TEM /nm	Reduction peak area^e
40Cu/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 are calculated by ICP-OES; ^b: copper content of the used catalysts after calcination are 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
Catalysts	Cu 2p_3/2	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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