双金属氧化物 Co3AlOx 催化糠醛加氢制备糠醇

doi:10.3969/j.issn.0253-2417.2022.05.002

林产化学与工业 ›› 2022, Vol. 42 ›› Issue (5): 8-14.doi: 10.3969/j.issn.0253-2417.2022.05.002

双金属氧化物 Co₃AlO_x 催化糠醛加氢制备糠醇

姜伟¹(), 辛颖¹, 巩明月¹, 王伟众¹, 王东军¹, 孙勇²^,*()

1. 中国石油石油化工研究院大庆化工研究中心，黑龙江大庆 163714
2. 厦门大学能源学院；福建省生物质清洁高值化技术工程研究中心；厦门市生物质清洁高值化利用重点实验室，福建厦门 361102

收稿日期:2021-07-30 出版日期:2022-10-28 发布日期:2022-11-02
通讯作者: 孙勇 E-mail:jiangwei459@petrochina.com.cn;sunyong@xmu.edu.cn
作者简介:孙勇，教授，博士生导师，研究领域为生物质化学品与材料；E-mail: sunyong@xmu.edu.cn
姜伟(1988—)，男，河北承德人，高级工程师，从事石油化工及生物质综合利用方面研究；E-mail: jiangwei459@petrochina.com.cn
基金资助:
国家自然科学基金资助项目(21776234)

Catalytic Hydrogenation of Furfural to Furfuryl Alcohol Using Co₃AlO_x

Wei JIANG¹(), Ying XIN¹, Mingyue GONG¹, Weizhong WANG¹, Dongjun WANG¹, Yong SUN²^,*()

1. China Petroleum Petrochemical Research Institute Daqing Petrochemical Research Center, Daqing 163714, China
2. College of Energy, Xiamen University; Fujian Engineering and Research Center of Clean and High-valued Technologies for Biomass; Xiamen Key Laboratory of Clean and High-valued Utilization for Biomass, Xiamen 361102, China

Received:2021-07-30 Online:2022-10-28 Published:2022-11-02
Contact: Yong SUN E-mail:jiangwei459@petrochina.com.cn;sunyong@xmu.edu.cn

摘要/Abstract

摘要：

合成了Co/Al双金属氧化物催化剂，并将其用于催化还原糠醛制备糠醇。通过调节Co/Al的物质的量之比，探讨了活性金属的比例对催化剂物理、化学性质的影响。N₂吸附/脱附等温线分析表明，制备得到的系列Co_xAlO_y催化剂为平均孔径20 nm左右的介孔材料；NH₃-TPD分析表明，中等强度酸位点占主导有利于糠醛加氢制糠醇。Co/Al物质的量比3∶1时制得的催化剂Co₃AlO_x表现出优异的催化活性，在反应物0.3 g糠醛、溶剂20 mL 1, 4-二氧六环、催化剂Co₃AlO_x用量0.12 g，反应时间3 h，H₂压力2 MPa，反应温度120 ℃条件下，糠醛转化率超过98.95%，糠醇得率可以达到96.25%。XRD、TEM和XPS分析表明：Co₃AlO_x以CoAl₂O₄和Co₂O₃的混合相形式存在，比表面积和中等强度酸是影响催化活性的关键因素。Co₃AlO_x催化剂经过5次循环实验后，催化活性仍能保持83.13%，具有十分良好的循环稳定性。

关键词: 糠醛, 糠醇, 催化还原, 钴铝双金属氧化物

Abstract:

Co/Al bimetallic oxide catalyst was prepared and used for catalytic reduction of furfural to furfuryl alcohol. The effects of the active metal ratio on the physical and chemical properties of the catalyst were discussed by adjusting the molar ratio of Co/Al. N₂ adsorption/desorption analysis showed that the series of prepared Co_xAlO_y catalysts were mesoporous materials with an average pore size of about 20 nm. NH₃-TPD analysis showed that the dominance of moderate acid sites was favorable for hydrogenation of furfural to furfuryl alcohol. The prepared Co₃AlO_x with the Co/Al molar ratio of 3∶1 exhibited excellent catalytic activity. Under the operational conditions of 0.3 g furfuryl alcohol, 20 mL solvent 1, 4-dioxane, 0.12 g catalyst Co₃AlO_x, reaction time 3 h, H₂ pressure 2 MPa and reaction temperature 120 ℃, the conversion of furfuryl alcohol was more than 98.95%, and the yield of furfuryl alcohol could reach 96.25%. XRD, TEM and XPS analysis showed that Co₃AlO_x existed in the mixed phase of CoAl₂O₄ and Co₂O₃, and the specific surface area and moderate acid strength were the key factors determining the catalytic activity. The catalytic activity of Co₃AlO_x catalyst could still maintain 83% after 5 cycles, which indicates its good cycle stability.

Key words: furfural, furfuryl alcohol, catalytic reduction, Co/Al bimetallic oxide

中图分类号:

TQ35

姜伟, 辛颖, 巩明月, 王伟众, 王东军, 孙勇. 双金属氧化物 Co₃AlO_x 催化糠醛加氢制备糠醇[J]. 林产化学与工业, 2022, 42(5): 8-14.

Wei JIANG, Ying XIN, Mingyue GONG, Weizhong WANG, Dongjun WANG, Yong SUN. Catalytic Hydrogenation of Furfural to Furfuryl Alcohol Using Co₃AlO_x[J]. Chemistry and Industry of Forest Products, 2022, 42(5): 8-14.

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参考文献 21

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催化剂 catalyst	糠醛转化率/% FFR conversion	选择性 selectivity/%			糠醇得率/% FFA yield
催化剂 catalyst	糠醛转化率/% FFR conversion	MF	FFA	副产物 byproduct	糠醇得率/% FFA yield
CoO_x	64.37	3.21	67.50	6.52	43.45
AlO_x	22.51	—	—	—	0
CoAlO_x	98.32	2.24	89.93	7.80	88.42
Co₂AlO_x	96.37	1.00	97.74	1.23	94.23
Co₃AlO_x	98.95	1.84	97.22	0.94	96.25
Co₄AlO_x	93.28	7.20	91.80	1.00	85.63
Co₅AlO_x	89.62	8.12	90.52	1.36	81.12
Co₆AlO_x	86.50	10.40	88.70	1.16	76.72

催化剂 catalyst	比表面积/(m²·g^-1) S_BET	孔体积/(cm³·g^-1) V_pore	孔径/nm D_pore	酸度 acidity/(mmol·g^-1)
催化剂 catalyst	比表面积/(m²·g^-1) S_BET	孔体积/(cm³·g^-1) V_pore	孔径/nm D_pore	弱酸 weak	中强酸 medium	强酸 strong	总酸度 total acidity
Co₂AlO_x	47.75	0.229	19.1	0.040	0.130	0.005	0.175
Co₃AlO_x	45.40	0.249	21.9	0.025	0.128	0.003	0.156
Co₄AlO_x	47.15	0.225	19.1	0.022	0.127	0.023	0.172
Co₅AlO_x	36.86	0.182	19.8	0.032	0.148	0.035	0.215
Co₆AlO_x	31.95	0.166	20.7	0.031	0.171	0.023	0.225

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双金属氧化物 Co₃AlO_x 催化糠醛加氢制备糠醇

Catalytic Hydrogenation of Furfural to Furfuryl Alcohol Using Co₃AlO_x

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