5-羟甲基糠醛催化氢化制备2, 5-二羟甲基呋喃

doi:10.3969/j.issn.0253-2417.2022.06.004

摘要/Abstract

摘要：

以乙醇为氢供体和溶剂，以炭化蔗渣(CBD)负载铜和锌纳米颗粒(Cu-Zn/CBD)作催化剂，研究了5-羟甲基糠醛(HMF)催化氢化制备2, 5-二羟甲基呋喃(BHMF)。考察了催化剂金属比例、反应温度、反应时间等对HMF催化氢化反应的影响。采用XRD、SEM和TEM对催化剂表面形态及结构进行了表征，利用XPS和ICP-OES对催化剂的元素价态及含量进行了分析，并采用HPLC对反应后混合液进行分析。研究结果表明：与单金属Cu/CBD、Zn/CBD相比，双金属Cu-Zn/CBD具有较高的催化活性；当金属Cu/Zn质量比为2∶1，在反应温度为160 ℃、反应时间为1.5 h的最佳条件下，HMF的转化率为86.5%，BHMF的产率为82.5%。催化剂的重复使用性能较好，重复使用5次后，少量的Cu和Zn纳米颗粒损失导致HMF转化率和BHMF产率分别下降为77.3%和76.8%。

关键词: 5-羟甲基糠醛, 2, 5-二羟甲基呋喃, 氢供体, Cu-Zn/CBD

Abstract:

The catalytic hydrogenation of 5-hydroxymethylfurfural(HMF) for preparation of 2, 5-bishydroxymethylfuran(BHMF) was studied, using ethanol as hydrogen donor and solvent, and copper and zinc nanoparticles(Cu-Zn/CBD) supported by carbonized sugarcane bagasse(CBD) was used as catalyst. The effects of reaction parameters such as catalyst metal proportion, reaction temperature and reaction time on the reaction of HMF hydrogenation were investigated. The surface morphology and structure of the catalyst were characterized by XRD, SEM and TEM. The elemental valence and content of the catalyst were analyzed by XPS and ICP-OES, and mixture after reaction was analyzed by HPLC. The results showed that the bimetallic Cu-Zn/CBD catalyst exhibited higher catalytic activity than those of single metal catalyst Cu/CBD and Zn/CBD. Under the optimal conditions of the Cu/Zn mass ratio of 2∶1, the reaction temperature of 160 ℃, and the reaction time of 1.5 h, the conversion rate of HMF was 86.5%, and the yield of BHMF was 82.5%. The reusability of catalysts was excellent. After recycling for 5 times, owing to the loss of a small amount of Cu and Zn nanoparticles, the conversion rate HMF and yield of BHMF decreased to 77.3% and 76.8%, respectively.

Key words: HMF, BHMF, hydrogen donor, Cu-Zn/CBD

中图分类号:

TQ35

甘甜, 张凯莉, 叶科, 刘颖, 武书彬, 庄军平. 5-羟甲基糠醛催化氢化制备2, 5-二羟甲基呋喃[J]. 林产化学与工业, 2022, 42(6): 24-30.

Tian GAN, Kaili ZHANG, Ke YE, Ying LIU, Shubin WU, Junping ZHUANG. Catalytic Hydrogenation of 5-Hydroxymethyl-furfural into 2, 5-Bishydroxymethylfuran[J]. Chemistry and Industry of Forest Products, 2022, 42(6): 24-30.

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样品¹⁾ samples	质量分数mass fraction/%							S_BET/(m²·g^-1)
样品¹⁾ samples	C	H	O	N	S	Cu	Zn	S_BET/(m²·g^-1)
蔗渣bagasse	38.60	6.47	54.49	0.40	0.04	—	—	9.65
CBD	67.25	3.27	28.68	0.78	0.02	—	—	11.30
Cu-Zn/CBD-0	65.92	3.27	25.87	0.84	0.02	2.52	1.56	10.90
Cu-Zn/CBD-5	65.11	3.15	27.23	0.85	0.02	2.35	1.29	9.78

编号 No.	催化剂 catalyst	HMF转化率/% HMF conversion	BHMF产率/% BHMF yield
1	CBD	—	—
2	Cu/CBD	70.6	36.2
3	Zn/CBD	21.0	—
4	Cu-Zn(1∶1)/CBD	79.1	63.7
5	Cu-Zn(2∶1)/CBD	89.0	83.0
6	Cu-Zn(1∶2)/CBD	16.9	—

使用次数 using number	HMF转化率/% HMF conversion	BHMF产率/% BHMF yield
1	86.5	82.5
2	84.0	81.9
3	83.8	81.7
4	82.1	81.6
5	77.3	76.8

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