超重力强化O3/H2O2氧化甲苯合成苯甲酸的研究

doi:10.11949/0438-1157.20190952

摘要/Abstract

摘要：

提出一种超重力环境下甲苯合成苯甲酸的新方法，对比不同臭氧化工艺合成苯甲酸的收率，研究了反应溶剂、臭氧气相浓度、过氧化氢与甲苯的摩尔比、超重力因子、液体流量对苯甲酸收率的影响规律。研究结果表明：RPB (rotating packed bed)-O₃/H₂O₂较其他工艺具有更高的反应性能；得到优化的工艺条件是反应溶剂为乙腈、臭氧气相浓度为80 mg·L^-1、过氧化氢与甲苯的摩尔比为0.15、超重力因子为40、液体流量为120 L·h^-1，在优化的工艺条件下得到苯甲酸收率为45%。通过电子顺磁共振仪 (EPR)对反应过程中产生的活性自由基进行表征，结果表明，O₃/H₂O₂体系中存在·OH。另外，用气相色谱-质谱联用仪(GC-MS)分析了中间产物，结果表明反应过程中生成的中间产物包括苯甲醇和苯甲醛。基于ERP实验和GC-MS表征结果，探索臭氧/双氧水氧化甲苯合成苯甲酸可能的反应历程。

关键词: 甲苯, 苯甲酸, 旋转填料床, 臭氧, 双氧水, 羟基自由基

Abstract:

The synthesis of benzoic acid using ozone combined with hydrogen peroxide in a rotating packed bed (RPB) was proposed in this study. Firstly, the process (RPB-O₃/H₂O₂) was compared with other ozonation processes, such as BR (bubbling reactor)-O₃/H₂O₂，RPB-O₃，BR-O₃, and RPB-O₃/H₂O₂ exhibited higher oxidation property for the synthesis of benzoic acid. Secondly, effects of different operating conditions including solvents, ozone gas concentration, molar ratio of hydrogen peroxide to toluene, high gravity factor, liquid flow rate, solvents and reaction time were investigated. The results revealed that the optimal operation conditions were solvent of acetonitrile, the ozone gas concentration of 80 mg·L^-1, molar ratio of hydrogen peroxide to toluene 0.15, high gravity factor of 40, liquid ?ow rate of 120 L·h^-1. Under the optimal conditions, the benzoic acid is obtained in 45% yield. The active radical generated in the reaction process was characterized by electron paramagnetic resonance (EPR), and ·OH was only found. Besides, the main intermediates of benzyl alcohol and benzaldehyde were identified by gas chromatography-mass spectrometry (GC-MS). Based on the results of ERP experiment and GC-MS characterization, the possible reaction process of benzoic acid synthesis by oxidation of toluene with ozone / hydrogen peroxide was explored.

Key words: toluene, benzoic acid, rotating packed bed, ozone, hydrogen peroxide, hydroxyl radical

中图分类号:

TQ 245.1

高文强, 焦纬洲, 刘有智. 超重力强化O₃/H₂O₂氧化甲苯合成苯甲酸的研究[J]. 化工学报, 2020, 71(3): 1045-1052.

Wenqiang GAO, Weizhou JIAO, Youzhi LIU. Oxidation of toluene to benzoic acid by O₃/H₂O₂ process enhanced usinghigh-gravity technology[J]. CIESC Journal, 2020, 71(3): 1045-1052.

图/表 12

表1 RPB反应器相关参数

Table 1 Equipment parameters of RPB

参数	数值
填料外径	75 mm
填料内径	40 mm
填料轴向高度	75 mm
比表面积	935.07 m²·m^-3
填料密度	7.9 g·cm^-3
孔隙率	0.74

图1 实验工艺流程1—氧气钢瓶；2—臭氧发生器；3—气体流量计；4—旋转填料床；5—液体流量计；6—液泵；7—储液槽；8—尾气处理装置；9—气相臭氧浓度检测仪

Fig.1 Schematic diagram of experimental setup

图2 不同臭氧化工艺的对比(超重力因子β=40; 液体流量: 100 L·h-1; 双氧水的投加量为: 0.7 ml; 臭氧气相浓度为: 80 mg·L-1; 溶剂: 乙腈)

Fig.2 Comparison of different ozonation processes

图3 反应溶剂对苯甲酸收率的影响以及臭氧在不同溶剂中的溶解度(超重力因子β=40; 液体流量: 100 L·h-1; 双氧水的投加量为: 0.7 ml; 臭氧气相浓度为: 80 mg·L-1; 反应时间: 60 min)

Fig.3 Effect of reaction solvents on yield of benzoic acid and solubility of ozone in different solvents

图4 臭氧气相浓度对苯甲酸收率的影响(液体流量: 100 L·h-1; 双氧水的投加量为: 0.7 ml; 溶剂: 乙腈; 反应时间: 60 min)

Fig. 4 Effect of ozone gas concentration on yield of benzoic acid

图5 双氧水的投加量对苯甲酸收率的影响(超重力因子β=40; 液体流量: 100 L·h-1; 臭氧气相浓度为: 80 mg·L-1; 溶剂: 乙腈; 反应时间: 60 min)

Fig. 5 Effect of H2O2 dosage on yield of benzoic acid

图6 液体流量对苯甲酸收率的影响(双氧水的投加量为: 1.0 ml; 臭氧气相浓度为: 80 mg·L-1; 溶剂: 乙腈; 反应时间: 60 min)

Fig.6 Effect of liquid flow rate on yield of benzoic acid

图7 超重力因子对苯甲酸收率以及RPB气体出口臭氧浓度的影响(双氧水的投加量为: 1.0 ml; 臭氧气相浓度为: 80 mg·L-1; 溶剂: 乙腈; 反应时间: 60 min)

Fig.7 Effect of high gravity factor on yield of benzoic acid and ozone concentration at gas outlet of RPB

图8 RPB-O3/H2O2体系中的EPR光谱图

Fig.8 EPR spectra of radical species in RPB-O3/H2O2

图9 GC-MS分析O3/H2O2体系合成苯甲酸的色谱图

Fig.9 GC-MS chromatograms for synthesis of benzoic acid by O3/H2O2 system

表2 GC-MS分析O3/H2O2体系氧化甲苯的中间产物

Table 2 Intermediate products of O3/H2O2 system by GC-MS

序号	保留时间/min	化合物	质谱(m/z)
1	4.464～4.858	苯甲醛	106.0
2	5.484～5.634	苯甲醇	108.1
3	6.931～7.310	苯甲酸	122.0

图10 O3/H2O2氧化甲苯合成苯甲酸可能的反应历程

Fig.10 Proposed pathways of oxidation of toluene to benzoic acid by O3/H2O2 process

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超重力强化O₃/H₂O₂氧化甲苯合成苯甲酸的研究

Oxidation of toluene to benzoic acid by O₃/H₂O₂ process enhanced usinghigh-gravity technology

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