离子液体催化合成2-氰基呋喃反应动力学研究

doi:10.11949/0438-1157.20230255

摘要/Abstract

摘要：

2-氰基呋喃（CF）是一种具有广泛潜在应用的重要生物基衍生物，是合成糠胺、糠酸等产品的关键原料，但目前对于合成2-氰基呋喃的研究甚少。本研究采用离子液体为催化剂，探究了糠醛与离子液体型羟胺盐反应制备2-氰基呋喃的动力学过程。考察了反应温度和反应时间对产物收率的影响，建立了反应动力学模型，对动力学参数进行了有效性验证。实验结果显示：当反应温度为120℃，反应时间为2 h时，糠醛转化率和2-氰基呋喃收率均为100%。通过计算得到了活化能、指前因子及动力学方程，对比了计算值和实验值，发现平均误差为0.34%，从而验证了该反应动力学方程的准确性，为2-氰基呋喃的后续应用提供了理论指导。

关键词: 生物质, 2-氰基呋喃, 糠醛, 离子液体, 动力学

Abstract:

2-Cyanofuran (CF) is an important bio-based derivative with a wide range of potential applications. It is a key raw material for the synthesis of furfurylamine, furoic acid and other products, but there are few studies on the synthesis of 2-cyanofuran. In this study, ionic liquid was used as catalyst to explore the kinetic process of preparing 2-cyanofuran by reaction of furfural and hydroxylamine ionic liquid salt. The effect of reaction temperature and reaction time on the product yield was investigated. The kinetic model was established, and the kinetic parameters were validated. The experimental results showed that the furfural conversion and 2-cyanofuran yield were 100% when the reaction temperature is 120℃ and the reaction time was 2 h. The activation energy, pre-exponential factor and kinetic equation were obtained by calculation. By comparing the calculated and experimental values, it was found that the average error was 0.34%, which verified the accuracy of the kinetic equation and provided theoretical guidance for the subsequent application of 2-cyanofuran.

Key words: biomass, 2-cyanofuran, furfural, ionic liquid, dynamics

中图分类号:

TQ 013.2

郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.

Jiali ZHENG, Zhihui LI, Xinqiang ZHAO, Yanji WANG. Kinetics of ionic liquid catalyzed synthesis of 2-cyanofuran[J]. CIESC Journal, 2023, 74(9): 3708-3715.

图/表 15

图1 2-氰基呋喃的绿色合成

Fig.1 Green synthesis of 2-cyanofuran

图2 (NH2OH)2·[HSO3-b-mim]·HSO4的合成

Fig.2 Synthesis of (NH2OH)2·[HSO3-b-mim]·HSO4

图3 [HSO3-b-mim]·HSO4和 (NH2OH)2·[HSO3-b-mim]·HSO4的红外光谱图

Fig.3 Infrared spectra of [HSO3-b-mim]·HSO4 and (NH2OH)2·[HSO3-b-mim]·HSO4

图4 [HSO3-b-mim]·HSO4和 (NH2OH)2·[HSO3-b-mim]·HSO4的核磁谱图

Fig.4 1H NMR spectra and 13C NMR spectra of [HSO3-b-mim]·HSO4 and (NH2OH)2·[HSO3-b-mim]·HSO4

图5 反应时间对2-氰基呋喃合成的影响reaction conditions: FF 3.6 mmol, n (FF)∶n[(NH2OH)2·[HSO3-b-mim]·HSO4] = 1∶1.5, paraxylene 8 ml, [HSO3-b-mim]·HSO4 4 ml, 120℃

Fig.5 Effect of reaction time on synthesis of 2-cyanofuran

图6 反应温度对2-氰基呋喃合成的影响reaction conditions: FF 3.6 mmol, n (FF)∶n[(NH2OH)2·[HSO3-b-mim]·HSO4] = 1∶1.5, 2 h, paraxylene 8 ml, [HSO3-b-mim]·HSO4 4 ml

Fig.6 Effect of reaction temperature on synthesis of 2-cyanofuran

图7 不同温度下的YCF-t曲线reaction conditions: FF 3.6 mmol, n (FF)∶n[(NH2OH)2·[HSO3-b-mim]·HSO4] = 1∶1.5, paraxylene 8 ml, [HSO3-b-mim]·HSO4 4 ml

Fig.7 YCF-t curves at different temperatures

图8 不同温度下的XFF-t曲线reaction conditions: FF 3.6 mmol, n (FF)∶n[(NH2OH)2·[HSO3-b-mim]·HSO4] = 1∶1.5, paraxylene 8 ml, [HSO3-b-mim]·HSO4 4 ml

Fig.8 XFF-t curves at different temperatures

图9 搅拌速度对转化率的影响

Fig.9 Effect of stirring speed on conversion

表1 不同温度体系下不同时刻反应转化率及积分值Ii

Table 1 Conversion and Ii at different time under different temperature systems

温度/K	反应时间/min	反应转化率/%	积分值Ii/(L/mol)
353.15	5	16.67	0.42
	15	36.06	1.06
	25	50.49	1.73
	35	67.44	2.89
	45	75.40	3.71
	65	89.20	5.46
	90	93.23	7.74
	95	94.26	8.27
363.15	5	16.30	0.41
	15	48.87	1.64
	25	68.93	3.03
	40	80.99	4.49
	50	87.43	5.77
	60	93.50	7.03
	80	95.72	9.22
	85	96.09	9.52
	90	96.31	9.70
368.15	5	24.56	0.65
	10	44.68	1.44
	15	62.23	2.47
	30	89.41	4.20
	40	94.78	5.72
	50	96.18	6.40
	55	97.00	6.94
	70	97.18	9.70
	80	97.65	11.18
	85	97.82	11.44
	90	97.96	11.65
373.15	5	53.48	1.51
	10	65.37	1.81
	25	91.08	4.57
	40	96.06	6.33
	45	96.40	6.52
	60	97.64	9.12
	70	97.70	11.26
	75	97.90	11.56
	80	98.09	11.88
	85	98.26	12.19

图10 不同温度下Ii-t关系

Fig.10 Ii-t relationship at different temperatures

表2 线性拟合方程

Table 2 Linear fitting equation

温度T/K	拟合方程	R²
353.15	y=0.086x	0.999
363.15	y=0.112x	0.999
368.15	y=0.134x	0.998
373.15	y=0.151x	0.995

表3 不同温度体系下的lnk值

Table 3 lnk value at different temperature systems

温度T/K	T^-1/K^-1	k/(L/(min∙mol))	lnk
353.15	0.00283	0.086	-2.453
363.15	0.00275	0.112	-2.189
368.15	0.00272	0.134	-2.010
373.15	0.00268	0.151	-1.890

图11 反应速率常数和温度的关系

Fig.11 Relationship between apparent reaction rate constant and temperature

表4 110℃下糠醛转化率计算值与实验值的比较

Table 4 Comparison of calculated value and measured value of furfural conversion at 110℃

t/min	X_cal/%	X_exp/%	δ/%
70	98.98	99.56	0.64
80	99.40	99.55	0.15
90	99.67	99.53	-0.14
100	99.81	99.51	-0.30
110	99.89	99.51	-0.38
120	99.94	99.50	-0.44

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