CuO-WO3-ZrO2的结构和性质对苯甲醛加氢反应催化性能的影响

doi:10.7503/cjcu20180757

摘要/Abstract

摘要：

采用共沉淀法制备了不同CuO和WO₃含量的CuO-WO₃-ZrO₂催化剂. 利用X射线衍射(XRD)、扫描电子显微镜(SEM)、 X射线荧光光谱(XRF)、 N₂气物理吸附、氢气程序升温还原(H₂-TPR)、 X射线光电子能谱(XPS)及程序升温脱附(TPD)等手段对催化剂的结构和表面性质进行了表征. 结果表明, WO₃的引入可以调变ZrO₂的晶型, 从而使催化剂的比表面积和孔径发生变化, 促进CuO在催化剂表面的分散, 并影响催化剂的酸碱性. 在苯甲醛加氢制备苯甲醇反应中, 以CuO质量分数为18%, WO₃质量分数为10%的CuO-WO₃-ZrO₂为催化剂时苯甲醛单程转化率达到92.03%, 产物苯甲醇的选择性为94.76%.

关键词: CuO-WO₃-ZrO₂催化剂, 加氢, 苯甲醇, 苯甲醛

Abstract:

CuO-WO₃-ZrO₂ catalysts were prepared by co-precipitation method. Structures and surface properties of the catalysts were characterized by X-ray powder diffraction(XRD), scanning electron microscope(SEM), X-ray fluorescence(XRF), N₂ physisorption, temperature programmed hydrogen reduction(H₂-TPR), X-ray photoelectron spectroscopy(XPS) and temperature programmed desorption(TPD). Addition of WO₃ into CuO-ZrO₂ induced the transformation of ZrO₂ from monoclinic to tetragonal phases, improved the dispersion of CuO species, changed the acid-base properties of the catalysts as well as the catalyst textural features such as surface area and the average pore diameter. As a consequence, the catalytic performance for the hydrogenation of benzaldehyde to benzyl alcohol was greatly promoted by the introduction of WO₃. For the optimal catalyst containing 10%(mass fraction) CuO and 18%(mass fraction) WO₃, the conversion of benzaldehyde and the selectivity to benzyl alcohol reached 94.76% and 92.03%, respectively.

Key words: CuO-WO₃-ZrO₂ Catalyst, Hydrogenation, Benzyl alcohol, Benzaldehyde

中图分类号:

O643
O625

TrendMD:

黄锐, 姚志龙, 孙培永, 张胜红. CuO-WO₃-ZrO₂的结构和性质对苯甲醛加氢反应催化性能的影响. 高等学校化学学报, 2019, 40(5): 1005.

HUANG Rui,YAO Zhilong,SUN Peiyong,ZHANG Shenghong. Effect of Structure and Properties of CuO-WO₃-ZrO₂ on Hydrogenation Catalytic of Benzaldehyde^†. Chem. J. Chinese Universities, 2019, 40(5): 1005.

图/表 15

Fig.1 XRD patterns of catalysts with different WO3 contents a. 18CuO-12WO3-ZrO2; b. 18CuO-10WO3-ZrO2; c. 18CuO-8WO3-ZrO2; d. 18CuO-6WO3-ZrO2; e. 18CuO-4WO3-ZrO2; f. 18CuO-0WO3-ZrO2.

Fig.2 H2-TPR profiles of catalysts with different WO3 contentsa. 18CuO-14WO3-ZrO2; b. 18CuO-12WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 18CuO-8WO3-ZrO2; e. 18CuO-6WO3-ZrO2; f. 18CuO-4WO3-ZrO2; g. 18CuO-0WO3-ZrO2.

Table 1 Textural properties of catalysts with different WO3 contents

Catalyst				Catalyst
18CuO-0WO₃-ZrO₂	0.00	10.3	16.91	18CuO-10WO₃-ZrO₂	9.83	35.5	8.95
18CuO-4WO₃-ZrO₂	3.25	19.8	15.37	18CuO-12WO₃-ZrO₂	10.86	36.3	8.50
18CuO-6WO₃-ZrO₂	5.80	25.9	10.77	18CuO-14WO₃-ZrO₂	11.42	37.0	8.37
18CuO-8WO₃-ZrO₂	8.08	31.5	9.60

Fig.3 Cu2p XPS spectra of catalysts with different WO3 contentsa. 18CuO-10WO3-ZrO2; b. 18CuO-6WO3-ZrO2; c. 18CuO-0WO3-ZrO2.

Fig.4 CO2-TPD profiles of catalysts with different WO3 contentsa. 18CuO-14WO3-ZrO2; b. 18CuO-12WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 18CuO-8WO3-ZrO2; e. 18CuO-6WO3-ZrO2.

Fig.5 XRD patterns of catalysts with different CuO contents a. 24CuO-10WO3-ZrO2; b. 21CuO-10WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 15CuO-10WO3-ZrO2; e. 12CuO-10WO3-ZrO2; f. 0CuO-10WO3-ZrO2.

Fig.6 H2-TPR profiles of catalysts with different CuO contentsa. 24CuO-10WO3-ZrO2; b. 21CuO-10WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 15CuO-10WO3-ZrO2; e. 12CuO-10WO3-ZrO2; f. 0CuO-10WO3-ZrO2.

Table 2 Textural properties of catalysts with different CuO contents

Catalyst	Surface area/(m²·g^-1)	Average pore diameter/nm	Catalyst	Surface area/(m²·g^-1)	Average pore diameter/nm
12CuO-10WO₃-ZrO₂	36.4	9.02	21CuO-10WO₃-ZrO₂	33.0	9.96
15CuO-10WO₃-ZrO₂	36.4	9.68	24CuO-10WO₃-ZrO₂	32.2	9.39
18CuO-10WO₃-ZrO₂	35.5	8.95

Fig.7 SEM images of catalysts with different CuO contents(A) 12CuO-10WO3-ZrO2; (B) 18CuO-10WO3-ZrO2; (C) 24CuO-10WO3-ZrO2.

Fig.8 NH3-TPD profiles of catalysts with different CuO contentsa. 24CuO-10WO-ZrO23; b. 21CuO-10WO3-ZrO2; c. 18CuO-10WO3-ZrO2; d. 15CuO-10WO3-ZrO2; e. 12CuO-10WO3-ZrO2.

Table 3 Performance of catalysts with different WO3 contents*

w(WO₃)(%)	Conversion(%)	Selectivity(%)
w(WO₃)(%)	Conversion(%)	Benzyl alcohol	Benzyl benzoate	Diphenylmethane
0	60.38	90.85	0.28	Trace
4	79.34	89.24	0.46	1.06
6	84.07	90.28	1.25	1.01
8	88.99	90.89	1.33	0.97
10	94.76	92.03	1.59	0.97
12	94.08	92.17	0.74	0.96

Table 4 Performance of catalysts with different CuO contents*

w(CuO)(%)	Conversion(%)	Selectivity(%)
w(CuO)(%)	Conversion(%)	Benzyl alcohol	Toluene	Diphenylmethane	Benzene
0	15.56	42.38	1.45	Trace	Trace
12	47.61	92.70	1.96	0.98	0.22
15	81.80	90.96	2.68	0.98	0.23
18	94.76	92.03	4.34	0.97	0.20
21	74.42	90.52	2.58	0.89	0.22
24	66.93	96.36	2.05	0.87	0.21

Scheme 1 Plausible mechanism of 1,2 nucleophilic addition reaction

Fig.9 Effects of reaction temperature on catalytic performance of 12CuO-10WO3-ZrO2 for pincipal products

Scheme 2 Possible reaction pathways associated with the hydrogenation of benzaldehyde to the target benzyl alcohol and isolated byproducts(Ⅰ) Hydrogenation of benzaldehyde; (Ⅱ) hydrogenation of benzyl alcohol; (Ⅲ) decarburization of benzaldehyde; (Ⅳ) dehydrogenation and condensation of benzaldehyde and benzyl alcohol; (Ⅴ) alkylation of benzyl alcohol and benzene.

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CuO-WO₃-ZrO₂的结构和性质对苯甲醛加氢反应催化性能的影响

Effect of Structure and Properties of CuO-WO₃-ZrO₂ on Hydrogenation Catalytic of Benzaldehyde^†

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