微反应器内红色基KD重氮化反应动力学研究

doi:10.11949/0438-1157.20200741

摘要/Abstract

摘要：

重氮化反应是合成重氮盐中间体的传统方法，重氮盐中间体因其巨大的合成潜力，被广泛地应用于医药、农药、染颜料工业等精细化工领域。首先，利用重氮盐中间体的偶合反应以及紫外可见分光光度法建立了重氮盐中间体的定量方法，并且建立了用于红色基KD重氮化反应动力学参数测定的微反应器系统。在红色基KD低浓度以及远过量的盐酸浓度条件下，确定了该反应为二级反应，得到了反应的指前因子为1.57×10¹⁴ L/(mol·s)，活化能为 72.88 kJ/mol。在实验研究范围内建立了表观反应动力学模型，并且通过验证实验表明，模拟计算值与实验值吻合较好。

关键词: 微反应器, 微尺度, 反应动力学, 重氮化反应, 偶合反应, 偶氮染料

Abstract:

Diazotization reaction is a traditional method for synthesizing diazonium salt intermediates. Because of their huge synthesis potential, diazonium salt intermediates are widely used in fine chemical fields such as medicine, pesticides, dyeing and pigment industries. Firstly, the quantitative method of diazonium salt intermediates was established by the azo-coupling reaction and UV-visible spectrophotometry. Precision experiments and reproducibility experiments were performed for this measurement method. The results showed that the accuracy and reproducibility of the method were good, and the relative standard error was less than 1%, indicating that the method could be used in the quantitative study of diazonium salts. Then, a microreactor system for the determination of kinetic parameters of the diazotization reaction was established. Compared with the traditional batch reactor method, this method could strictly control the reaction conditions, such as reaction time and reaction temperature. Finally, under the condition of low red base KD concentration and far excess hydrochloric acid concentration, the reaction was determined to be a secondary reaction, and the pre-exponential factor of the reaction was 1.57×10¹⁴ L/(mol·s), and the activation energy was 72.88 kJ/mol. The reaction kinetics model was established within the experimental research scope, and the verification experiments showed that the simulation results were in good agreement with the experimental results.

Key words: microreactor, microscale, reaction kinetics, diazotization, coupling reaction, azo dye

中图分类号:

TQ 052.5

王法军, 黄晋培, 徐建鸿. 微反应器内红色基KD重氮化反应动力学研究[J]. 化工学报, 2021, 72(2): 984-992.

WANG Fajun, HUANG Jinpei, XU Jianhong. Kinetics of red base KD diazotization in microreactor system[J]. CIESC Journal, 2021, 72(2): 984-992.

图/表 16

图1 重氮化反应动力学参数测定装置

Fig.1 Experimental setup for determining kinetic parameters of the diazotization reaction

图2 膜分散微混合器的结构

Fig.2 Schematic diagram of the membrane dispersion microreactor

图3 重氮偶合反应方程式

Fig.3 The diazotization and coupling reaction

图4 偶氮染料A的紫外可见吸收光谱

Fig.4 UV-vis absorption curve of the azo dye standards A

图5 不同pH下波长变化

Fig.5 The changes in wavelength at different pH

图6 不同pH下吸光度的变化

Fig.6 The changes in absorbance at different pH values

图7 吸光度随浓度的变化

Fig.7 Concentration and absorbance linear relationship

表1 偶氮染料浓度测定方法的精密度实验结果

Table 1 Precision test results of concentration measurement of azo dye

样品编号	吸光度/A	浓度/(mg/L)	RSD/%
1	1.287	43.14	0.12
2	1.287	43.14
3	1.289	43.21
4	1.286	43.11
5	1.285	43.07

表2 偶氮染料浓度测定方法的重现性实验结果

Table 2 Reproducible test results of concentration measurement of azo dye

样品编号	吸光度/A	浓度/(mg/L)	RSD/%
1	1.286	43.11	0.69
2	1.286	43.11
3	1.279	42.87
4	1.302	43.65
5	1.283	43.01

图8 不同偶合组分与氢氧化钠的摩尔比下偶氮染料A的最大吸光度反应条件：反应温度（T）=20℃；重氮化反应停留时间（t）=167 s；溶液A与溶液B流量VA=VB=2.5 ml/min；溶液C流量VC=8 ml/min

Fig.8 Different absorbance at different molar ratio of coupling component to sodium hydroxide

图9 不同反应溶液流量下重氮化反应的收率反应条件：重氮化反应停留时间（t）=20 s；反应温度（T）=20℃

Fig.9 Yield of the diazotization reaction with different volume flow rate of the reactants

图10 温度和反应时间对反应物转化率的影响溶液A与溶液B流量VA=VB=2.5 ml/min；溶液C流量VC=8 ml/min

Fig.10 Effect of temperature and reaction time on reactant conversion

图11 不同温度下反应速率常数的拟合

Fig.11 Evaluation of reaction rate constants at different temperature

表3 不同温度下的反应速率常数

Table 3 Reaction rate constants at different temperatures

反应温度/℃	线性方程	R²	K/(L/(mol·s))
18	y= 0.0992x+0.0133	0.9918	13.22
14	y= 0.0653x+0.0459	0.9974	8.71
5	y= 0.0243x+0.0235	0.9976	3.24

图12 Arrhenius方程拟合结果

Fig.12 Fitting plot of Arrhenius equation

图13 特定温度下（10℃）下动力学模型验证反应温度(T)=10℃;溶液A与溶液B流量VA=VB=2.5 ml/min；溶液C流量VC=8 ml/min

Fig.13 Kinetic model verification at a specific reaction temperature

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