Pt/CaO材料催化糠醇加氢制备戊二醇

doi:10.16085/j.issn.1000-6613.2023-0448

化工进展 ›› 2024, Vol. 43 ›› Issue (3): 1318-1327.DOI: 10.16085/j.issn.1000-6613.2023-0448

• 工业催化 • 上一篇

Pt/CaO材料催化糠醇加氢制备戊二醇

萧垚鑫¹^,²(), 张军²^,³^,⁴(), 单锐²^,³^,⁴, 袁浩然²^,³^,⁴(), 陈勇¹^,²^,³^,⁴

^1.华南农业大学生物质工程研究院，广东广州 510642
^2.中国科学院广州能源研究所，广东广州 510640
^3.中国科学院可再生能源重点实验室，广东广州 510640
^4.广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640

收稿日期:2023-03-23 修回日期:2023-05-22 出版日期:2024-03-10 发布日期:2024-04-11
通讯作者: 袁浩然
作者简介:萧垚鑫（1998—），男，硕士研究生，研究方向为生物质高值资源化利用。E-mail：xiao19980129@yahoo.com
张军（1987—），男，博士，副研究员，研究方向为生物质/有机固废高值资源化利用。E-mail：zhangjun@ms.giec.ac.cn。
基金资助:
国家自然科学基金面上项目(51976222);能源清洁利用国家重点实验室开放基金(ZJU-CEU2020023);中国科学院青年创新促进会会员(2023367)

Catalytic hydrogenation of furfuryl alcohol into pentanediol over Pt/CaO materials

XIAO Yaoxin¹^,²(), ZHANG Jun²^,³^,⁴(), SHAN Rui²^,³^,⁴, YUAN Haoran²^,³^,⁴(), CHEN Yong¹^,²^,³^,⁴

^1.Institute of Biomass Engineering, South China Agricultural University, Guangzhou 510642, Guangdong, China
^2.Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences (CAS), Guangzhou 510640, Guangdong, China
^3.CAS Key Laboratory of Renewable Energy, Guangzhou 510640, Guangdong, China
^4.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China

Received:2023-03-23 Revised:2023-05-22 Online:2024-03-10 Published:2024-04-11
Contact: YUAN Haoran

摘要/Abstract

摘要：

通过浸渍法制备出一系列氧化钙负载铂金属催化材料，用于生物质基糠醇选择性加氢制备戊二醇研究。研究采用X射线衍射仪、扫描电子显微镜、CO₂-程序升温脱附、N₂等温吸附-脱附、X射线光电子能谱、热重-差热分析法等一系列表征手段，对合成的催化剂样品物理化学性质进行了系统表征。实验结果表明，Pt/CaO-600催化剂表现出优异的催化活性，在4MPa氢压、210℃反应温度条件下，糠醇转化率为99.8%，1,2-戊二醇和1,5-戊二醇收率分别可达48.6%和21.5%。催化剂的优异性能可归因于作为载体的CaO提供了适宜的碱性位点，有利于糠醇开环反应的发生，进而提高了糠醇转化率与戊二醇选择性。同时，催化剂还表现出了优异的循环使用性能，经重复使用4次后，其催化糠醇转化率可达96.5%，1,2-戊二醇和1,5-戊二醇的收率分别为40.3%和17.0%。

关键词: 糠醇, 催化, 加氢, 戊二醇

Abstract:

A series of Pt/CaO catalysts were synthesized via impregnation method and applied for the selective hydrogenation of bio-based furfuryl alcohol into pentanediol. The physicochemical characteristics of the as-prepared catalysts were comprehensively characterized through X-ray diffractometer, scanning electron microscopy, CO₂-temperature programmed desorption, N₂ isothermal adsorption-desorption, X-ray photoelectron spectroscopy, and thermogravimetric-differential thermal analysis. The experimental results showed that the Pt/CaO-600 catalyst exhibited excellent catalytic activity towards furfuryl alcohol hydrogenation. Gratifyingly, the furfuryl alcohol conversion achieved 99.8%, and the yields of 1,2-pentanediol and 1,5-pentanediol were 48.6% and 21.5% respectively at 210℃ under 4MPa H₂. The good activity of Pt/CaO could be attributed to the fact that the carrier CaO provided appropriate amounts of basic sites, which facilitated the ring-opening reaction of furfuryl alcohol, thus improving the conversion and pentanediol selectivity. Moreover, the as-prepared Pt/CaO also exhibited excellent performance in recycling experiments, wherein the yields of 1,2-pentanediol and 1,5-pentanediol reached 40.3% and 17.0% respectively with 96.5% furfuryl alcohol conversion after being repeated four times.

Key words: furfuryl alcohol, catalysis, hydrogenation, pentanediol

中图分类号:

TQ251.1

萧垚鑫, 张军, 单锐, 袁浩然, 陈勇. Pt/CaO材料催化糠醇加氢制备戊二醇[J]. 化工进展, 2024, 43(3): 1318-1327.

XIAO Yaoxin, ZHANG Jun, SHAN Rui, YUAN Haoran, CHEN Yong. Catalytic hydrogenation of furfuryl alcohol into pentanediol over Pt/CaO materials[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1318-1327.

图/表 17

图1 Pt/CaO-T样品XRD谱图

图2 Pt/CaO-T样品SEM图

图3 Pt/CaO-600样品TEM图

图4 Pt/CaO-600样品的TEM-mapping图

图5 Pt/CaO-T样品液氮吸附-脱附曲线

图6 Pt/CaO-T样品孔径分布

表1 催化剂结构信息和碱性参数

样品	比表面积/m²·g^-1	平均孔径/nm	孔容/cm³·g^-1	碱度/μmol·g^-1
Pt/CaO-400	48.47	23.70	0.29	37.59
Pt/CaO-500	93.62	19.75	0.46	50.14
Pt/CaO-600	76.72	17.46	0.33	55.45
Pt/CaO-700	5.70	19.48	0.002	63.45

图7 Pt/CaO-600样品XPS谱图

图8 Pt/CaO-T样品CO2-TPD脱附曲线

图9 Pt/CaO-T样品TG-DTA曲线

图10 催化剂煅烧温度对糠醇加氢反应影响

图11 糠醇加氢反应的气相色谱图（反应条件：糠醇0.6mmol，异丙醇15mL，190℃，2MPa H2，12h，600r/min，Pt/CaO-600 50mg）

图12 初始氢气压力对糠醇加氢转化影响

图13 反应温度对糠醇加氢转化影响

图14 反应时间对糠醇加氢转化影响

图15 催化剂循环性能测试

图16 Pt/CaO催化作用下糠醇选择性转化途径

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Pt/CaO材料催化糠醇加氢制备戊二醇

Catalytic hydrogenation of furfuryl alcohol into pentanediol over Pt/CaO materials

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