金属离子催化葡萄糖异构化和脱水反应特性研究

doi:10.3969/j.issn.1673-5854.2022.01.002

摘要/Abstract

摘要：

以金属氯化物为催化剂，研究金属离子对葡萄糖异构化和脱水反应的催化特性。考察金属离子种类、用量和温度对反应过程的影响，用动力学模型拟合实验数据，定量分析金属离子的催化规律。葡萄糖脱水制备HMF的反应是一个串联反应，基于此机理构建的动力学模型能准确描述各组分浓度随时间的变化。Ni²⁺、Cr³⁺和Sn⁴⁺具有良好的催化活性，但3种金属离子呈现不同的催化特性。Sn⁴⁺的葡萄糖转化速率最快，Ni²⁺最慢，但Sn⁴⁺的副反应速率常数是Ni²⁺的约20倍。实验范围内，增加Ni²⁺用量，葡萄糖异构化和副反应速率加快，但对果糖脱水过程没有催化活性。增加Cr³⁺用量能显著提升葡萄糖异构化速率，对其它反应影响不大。随着Sn⁴⁺用量的增大，各步反应速率均加快，但整个反应过程中的副反应的严重程度有所降低。反应速率常数随温度的变化规律遵循Arrhenius模型，对Ni²⁺而言，升高温度更能促进果糖副反应的发生；金属离子为Cr³⁺时，升高温度有利于果糖脱水生成HMF；而对于Sn⁴⁺，升高温度则更有利于葡萄糖的异构化。

关键词: 金属离子, 葡萄糖, 异构化, 果糖, 5-羟甲基糠醛

Abstract:

The catalytic characteristics of metal ions for glucose isomerization and dehydration were investigated with metal chloride as catalyst. The influences of metal ion category, content and temperature on reaction process were studied. The reaction kinetic model was applied to correlate experimental data to analyze catalytic characteristics quantitatively. The process of glucose to HMF was a tandem reaction, and the kinetic model based on this mechanism could simulate the reaction accurately. Ni²⁺, Cr³⁺ and Sn⁴⁺ possessed good catalytic activity for glucose conversion, among which the catalyst activity of Sn⁴⁺ was the highest, and that of Ni²⁺ was the lowest. The kinetic constant of side reaction of Sn⁴⁺ was about 20 times of that of Ni²⁺. For Ni²⁺, reaction rate of glucose isomerization and side reaction increased, yet the catalytic activity for fructose dehydration to HMF was negligible with the increasing of Ni²⁺ content. Increasing of Cr³⁺ could enhance reaction rate of glucose isomerization significantly, and almost had no effect on other reactions. With the increasing of Sn⁴⁺ content, reaction rate of all steps increased, yet the intensity of side reaction would decrease. The influence of temperature on reaction constants followed the Arrhenius model. Higher temperature was beneficial to the side reaction, fructose dehydration and glucose isomerization respectively, when Ni²⁺, Cr³⁺ and Sn⁴⁺ were used, respectively.

Key words: metal ion, glucose, isomerization, fructose, 5-hydroxymethylfurfural

中图分类号:

TQ35
TQ032.4

张永昭, 季佳佳, 汪洋, 李宏威, 刘松晖, 王文德. 金属离子催化葡萄糖异构化和脱水反应特性研究[J]. 生物质化学工程, 2022, 56(1): 7-12.

Yongzhao ZHANG, Jiajia JI, Yang WANG, Hongwei LI, Songhui LIU, Wende WANG. Catalytic Characteristics of Metal Ions for Glucose Isomerization and Dehydration[J]. Biomass Chemical Engineering, 2022, 56(1): 7-12.

图/表 7

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图3

参考文献 15

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离子 ion	葡萄糖转化率/% conversion	果糖产率/% fructose yield	HMF产率/% HMF yield	离子 ion	葡萄糖转化率/% conversion	果糖产率/% fructose yield	HMF产率/% HMF yield
Ni²⁺	18.5	9.1	0.0	Sn²⁺	64.5	0.7	0.0
Cr³⁺	17.5	6.8	1.5	Nb⁵⁺	80.0	0.0	0.2
Sn⁴⁺	50.3	0.4	4.9	Mn²⁺	6.0	0.0	0.0
Zn²⁺	4.6	2.6	0.0	Ce³⁺	3.8	3.9	0.0
Co²⁺	6.1	3.5	0.0	Fe³⁺	50.2	0.0	0.0
Cu²⁺	35.5	0.0	0.3	Fe²⁺	1.7	0.2	0.0
无none	3.1	0.0	0.0

金属离子 metal ion	用量/mol dosage	动力学参数kinetic parameters
金属离子 metal ion	用量/mol dosage	k₁/(kg·mol ^-1· min ^-1)	k₂/min ^-1	k₃/min ^-1
Ni²⁺	0.05	3.80×10^-3	0.00	1.15×10^-2
Ni²⁺	0.10	4.30×10^-3	0.00	1.62×10^-2
Cr³⁺	0.05	6.30×10^-3	3.38×10^-2	6.29×10^-2
Cr³⁺	0.10	8.80×10^-3	3.90×10^-2	7.05×10^-2
Sn⁴⁺	0.02	2.39×10^-2	1.03×10^-1	2.41×10^-1
Sn⁴⁺	0.04	3.81×10^-2	1.42×10^-1	2.84×10^-1

金属离子 metal ion	温度/K temperature	动力学参数kinetic parameters
金属离子 metal ion	温度/K temperature	k₁/(kg·mol ^-1· min ^-1)	k₂/min ^-1	k₃/min ^-1
Ni²⁺(0.1 mol)	363.15	2.09×10^-3	0	6.00×10^-3
	373.15	4.30×10^-3	0	1.62×10^-2
	383.15	5.82×10^-3	0	2.07×10^-2
Cr³⁺(0.1 mol)	363.15	6.55×10^-3	5.77×10^-3	2.90×10^-2
	373.15	8.80×10^-3	3.90×10^-2	7.05×10^-2
	383.15	2.32×10^-2	1.22×10^-1	1.53×10^-1
Sn⁴⁺(0.02 mol)	363.15	7.97×10^-3	3.07×10^-2	1.23×10^-1
	373.15	2.39×10^-2	1.03×10^-1	2.41×10^-1
	383.15	6.61×10^-2	1.35×10^-1	2.47×10^-1

离子 ion	反应活化能activation energy/(kJ·mol ^-1)
离子 ion	E_a ₁	E_a ₂	E_a ₃
Ni²⁺(0.1 mol)	59.37	—	71.69
Cr³⁺(0.1 mol)	72.79	176.93	96.24
Sn⁴⁺(0.02 mol)	122.37	86.14	40.38

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