化工学报 ›› 2023, Vol. 74 ›› Issue (9): 3708-3715.DOI: 10.11949/0438-1157.20230255
郑佳丽1(), 李志会1,2(), 赵新强1, 王延吉1()
收稿日期:
2023-03-17
修回日期:
2023-07-24
出版日期:
2023-09-25
发布日期:
2023-11-20
通讯作者:
李志会,王延吉
作者简介:
郑佳丽(1998—),女,博士研究生,2547124405@qq.com
基金资助:
Jiali ZHENG1(), Zhihui LI1,2(), Xinqiang ZHAO1, Yanji WANG1()
Received:
2023-03-17
Revised:
2023-07-24
Online:
2023-09-25
Published:
2023-11-20
Contact:
Zhihui LI, Yanji WANG
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。
中图分类号:
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
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 |
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 |
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 |
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 |
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 |
t/min | Xcal/% | Xexp/% | 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 |
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 | Xcal/% | Xexp/% | 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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