甲苯仿生催化氧化过程及卟啉合成工业应用研究
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摘要
本文以仿生催化应用于甲苯空气氧化制备苯甲醛与苯甲醇的过程为研究目的,采用自行设计的连续式氧化装置,考察了甲苯仿生催化连续氧化的反应规律,在有关仿生催化剂对甲苯氧化的影响方面获得了新的认识与结果；发现可以通过控制氧化反应工艺条件使甲苯仿生催化氧化在动力学与氧传递两种控制条件下发生反应,对动力学控制和氧传递控制下甲苯仿生催化氧化反应规律获得了新的认识与结果；根据甲苯生物循环与化学循环耦合反应过程机理,首次完整获得了甲苯仿生催化氧化反应动力学,定量的认识了仿生催化甲苯氧化过程各物质的转化规律,建立了甲苯仿生催化反应器模型,优化了甲苯仿生催化反应器与工艺条件,甲苯仿生催化氧化优化条件下的实验结果验证了模型的准确性与可靠性；以卟啉工业生产为研究对象,解决了卟啉生产过程中存在的关键工程问题,采用自行设计的卟啉工业化生产装置,首次成功高产率工业合成了四对氯苯基卟啉与对氯双铁卟啉,并改进了工业合成四苯基钴卟啉生产工艺。
本文围绕上述甲苯仿生催化氧化过程和卟啉合成工业应用中相关的问题,具体完成以下7个方面内容的研究：
1.研究了甲苯仿生催化连续氧化反应规律；在自行设计的连续反应装置中对甲苯仿生催化进行连续性氧化实验,考察了不同操作方式、金属卟啉催化剂对甲苯仿生催化氧化的影响,确定合适的甲苯仿生催化连续氧化的催化剂为对氯双铁卟啉,催化剂的浓度为2ppm；
2.为研究甲苯仿生催化氧化反应过程的控制步骤,针对甲苯仿生催化氧化反应体系的反应特征,设计了一套可以准确快速测定反应物氧在反应液中溶解浓度的装置；
3.研究了动力学控制和传质控制两种情况对甲苯仿生催化氧化的影响,发现动力学与传质控制条件下,反应转化率和选择性区别很大,同一反应时刻动力学控制较传质控制转化率高2-4%(moI)；在相同转化率时动力学控制目标产物苯甲醛和苯甲醇选择性较传质控制条件下转化率高8-10%(mo1)；结合甲苯仿生催化氧化反应机理和甲苯仿生催化氧化反应过程解释了上述实验现象；
4.研究了甲苯仿生催化氧化反应动力学,建立了甲苯仿生催化和化学催化耦合过程反应动力学模型；结合甲苯仿生催化氧化过程分析了动力学模型参数的物理意义；
5.在分批式甲苯仿生催化氧化反应中应用仿生催化氧化动力学模型,动力学模型模拟值与实验测量值相对标准偏差小于5%；获得了16个动力学模型参数,定量分析甲苯仿生催化和化学催化耦合过程关系；根据获得的甲苯仿生催化氧化各步反应活化能,解释了卟啉仿生催化过程中高选择性制备易于氧化的苯甲醛与苯甲醇的原因；
6.应用甲苯仿生催化氧化反应动力学,结合连续氧化反应器操作特征建立了甲苯仿生催化氧化反应器模型,优化了甲苯仿生催化氧化反应器,优化结果表明：三釜串联搅拌式全混反应器为适合甲苯仿生催化氧化较优的反应器组合形式。以苯甲醇苯甲醛产率为目标产物,控制目标产物选择性(50±3)%,优化的工艺条件为：三釜反应温度分别为463K,468K,473K；三釜平均停留时间为39min,30min,21min。苯甲醛与苯甲醇的产率为4.79%(mol),选择性为47.57%,甲苯转化率为10.07%(mol)；9L串联三釜连续甲苯氧化实验结果验证了模型的可靠性与准确性,实验数据与模型模拟值相对误差小于7.97%,平均相对误差为3.69%；
7.设计并安装了甲苯仿生催化氧化催化剂工业化生产装置,优化了四对氯苯基卟啉工业合成工艺,四对氯苯基卟啉的工业合成产率为31.90%优于实验室规模合成四对氯苯基卟啉和现有工业合成卟啉20%的产率；结合四苯基钴卟啉合成反应动力学与分批式操作反应器特征建立了四苯基钴卟啉合成反应器数学模型,改进了四苯基钻卟啉工业合成工艺条件,提高了四苯基钴卟啉合成产率与产品质量；研究了温度,反应体系初始PH值等关键的工艺因素对副产物对氯单铁卟啉转化为对氯双铁卟啉的影响,通过优化工艺参数控制副产物对氯单铁卟啉的形成,提高了对氯双铁卟啉工业合成产率与产品质量,四批对氯双铁卟啉工业实验合成产率>98.00%。
The process of toluene oxidation with air in the presence of metalloporphrin catalyst to produce benzaldehyde and benzyl alcohol has been studied in this paper. The design and installation of three stirred tank reactors in series as well as continuous experiments in laboratory scale have been carried out. The effect of metalloporphyrin catalyst on continuous oxidation of toluene as well as the influence of oxygen transfer limitations and kinetic control on biomimetic catalytic oxidation of toluene has been investigated. On basis of the biological-chemical-cycle coupling mechanism, the kinetics of biomimetic catalytic oxidation of toluene has been studied. And the corresponding kinetics mathematic model of toluene oxidation is developed firstly. Then by use of the kinetics model the experiment phenomena and the law of toluene oxidation have been analyzed quantitatively. According to the kinetics model several possible reactor models are established to optimize the oxidation reactor and reaction conditions for toluene oxidation in presence of metalloporphyrin. Finally the some chemical engineering problems of industrial synthesis of porphyrin are solved successfully. First industrial-scale synthesis of T(p-C1)PPH2and (T(p-C1)PPFe)2O has been carried out successfully in the plant designed by ourselves to produce porphyrin catalyst, and the process of industrial synthesis of cobaltporphyrin has been developed too. The main research works and results are as follows:
1. The liquid-phase catalytic aerobic oxidation of toluene by metalloporphyrin is studied in a series of three stirred tank reactors. The effects of operation mode(including batch and continuous operation), catalyst and optimal catalyst concentration on the oxidation process are examined. The conversion of toluene and the selectivity to benzaldehyde and benzyl alcohol are chosen as the evaluating index. The research results are:the best catalyst is (T(p-C1)PPFe)2O and its concentration is2ppm.
2. In order to determine the control step of toluene oxidation process accurately an improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperatures and pressures is used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin.
3. Under oxygen transfer limitations and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin is studied. The effect of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene are systematically investigated. The results show that the toluene conversion under the oxygen transfer limitations is lower by2～4%(mol) than that under kinetic control under same oxidation conditions. And the total selectivity of benzaldehyde and benzyl alcohol under the oxygen transfer limitations is lower by8～10%(mol) than that under kinetic control with the same conversion of toluene. The rate of oxygen transfer doesn't influence toluene conversion and the selectivity of benzaldehyde and benzyl alcohol under the kinetics control conditions, and toluene oxidation is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrin.
4. On basis of the biological-chemical-cycle coupling mechanism, the kinetics of biomimetic catalytic oxidation of toluene has been studied. And the corresponding kinetics mathematic model of toluene oxidation is developed firstly. Then by use of the kinetics model the physical meaning of model parameters are analyzed in detail according to the oxidation process of toluene.
5. The16kinetics model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a batch oxidation reactor where the gas and liquid phases are well mixed, and the standard deviation of the simulated and experimental data is less than5%. The biological-chemical-cycle coupling process of toluene oxidation is explained quantitatively, the reason of high selectivity to benzaldehyde and benzyl alcohol during the toluene oxidation in presence of metalloporphrin is explained successfully according the relation of reaction activation energy.
6. According to the kinetics model several possible reactor model are established to optimize the oxidation reactor and reaction conditions for toluene oxidation in presence of metalloporphyrin. The optimal results are:the conversion of toluene and the selectivity to benzaldehyde and benzyl alcohol is chosen as the evaluating index, the three continuous stirred tank reactors in series is appropriate for toluene oxidation; the optimal reaction temperature is463K,468K,473K each and average residence time of each is39min, 30min,21min; Under these reaction conditions the toluene conversion is10.07%(mol) and the selectivity to benzaldehyde and benzyl alcohol is47.57%(mol). By using the continuous mathematic reaction model for toluene oxidation with biomimetic catalyst, the maximal relative deviation between the experimental and calculated data is less than7.97%.The average relative deviation between the experimental and calculated data equals to3.69%.The reactor model predicted data for toluene oxidation systems agree with the experimental determined results satisfactorily.
7. The plant to produce porphyrin catalyst has been designed and installed. The process of industrial synthesis of T(p-C1)PPH2has been optimized.The results are:the yield of T(p-C1)PPH2can reach31.90%, while the yield is only about20%in laboratory; According to kinetics of synthesis of cobaltporphyrin, a batch reaction model for synthesis of cobaltporphyrin has been established, and by use of this model the optimal synthesis conditions have been obtained successfully. Under these optimal conditions the yield of the industrial synthesis of cobaltporphrin can reach98.00%; Final the effects of reaction temperature and PH on the yield for industrial synthesis of (T(p-C1)PPFe)2O has been investigated. And the yield for industrial synthesis of (T(p-C1)PPFe)2O is more than98.00%.
本文围绕上述甲苯仿生催化氧化过程和卟啉合成工业应用中相关的问题,具体完成以下7个方面内容的研究：
1.研究了甲苯仿生催化连续氧化反应规律；在自行设计的连续反应装置中对甲苯仿生催化进行连续性氧化实验,考察了不同操作方式、金属卟啉催化剂对甲苯仿生催化氧化的影响,确定合适的甲苯仿生催化连续氧化的催化剂为对氯双铁卟啉,催化剂的浓度为2ppm；
2.为研究甲苯仿生催化氧化反应过程的控制步骤,针对甲苯仿生催化氧化反应体系的反应特征,设计了一套可以准确快速测定反应物氧在反应液中溶解浓度的装置；
3.研究了动力学控制和传质控制两种情况对甲苯仿生催化氧化的影响,发现动力学与传质控制条件下,反应转化率和选择性区别很大,同一反应时刻动力学控制较传质控制转化率高2-4%(moI)；在相同转化率时动力学控制目标产物苯甲醛和苯甲醇选择性较传质控制条件下转化率高8-10%(mo1)；结合甲苯仿生催化氧化反应机理和甲苯仿生催化氧化反应过程解释了上述实验现象；
4.研究了甲苯仿生催化氧化反应动力学,建立了甲苯仿生催化和化学催化耦合过程反应动力学模型；结合甲苯仿生催化氧化过程分析了动力学模型参数的物理意义；
5.在分批式甲苯仿生催化氧化反应中应用仿生催化氧化动力学模型,动力学模型模拟值与实验测量值相对标准偏差小于5%；获得了16个动力学模型参数,定量分析甲苯仿生催化和化学催化耦合过程关系；根据获得的甲苯仿生催化氧化各步反应活化能,解释了卟啉仿生催化过程中高选择性制备易于氧化的苯甲醛与苯甲醇的原因；
6.应用甲苯仿生催化氧化反应动力学,结合连续氧化反应器操作特征建立了甲苯仿生催化氧化反应器模型,优化了甲苯仿生催化氧化反应器,优化结果表明：三釜串联搅拌式全混反应器为适合甲苯仿生催化氧化较优的反应器组合形式。以苯甲醇苯甲醛产率为目标产物,控制目标产物选择性(50±3)%,优化的工艺条件为：三釜反应温度分别为463K,468K,473K；三釜平均停留时间为39min,30min,21min。苯甲醛与苯甲醇的产率为4.79%(mol),选择性为47.57%,甲苯转化率为10.07%(mol)；9L串联三釜连续甲苯氧化实验结果验证了模型的可靠性与准确性,实验数据与模型模拟值相对误差小于7.97%,平均相对误差为3.69%；
7.设计并安装了甲苯仿生催化氧化催化剂工业化生产装置,优化了四对氯苯基卟啉工业合成工艺,四对氯苯基卟啉的工业合成产率为31.90%优于实验室规模合成四对氯苯基卟啉和现有工业合成卟啉20%的产率；结合四苯基钴卟啉合成反应动力学与分批式操作反应器特征建立了四苯基钴卟啉合成反应器数学模型,改进了四苯基钻卟啉工业合成工艺条件,提高了四苯基钴卟啉合成产率与产品质量；研究了温度,反应体系初始PH值等关键的工艺因素对副产物对氯单铁卟啉转化为对氯双铁卟啉的影响,通过优化工艺参数控制副产物对氯单铁卟啉的形成,提高了对氯双铁卟啉工业合成产率与产品质量,四批对氯双铁卟啉工业实验合成产率>98.00%。
The process of toluene oxidation with air in the presence of metalloporphrin catalyst to produce benzaldehyde and benzyl alcohol has been studied in this paper. The design and installation of three stirred tank reactors in series as well as continuous experiments in laboratory scale have been carried out. The effect of metalloporphyrin catalyst on continuous oxidation of toluene as well as the influence of oxygen transfer limitations and kinetic control on biomimetic catalytic oxidation of toluene has been investigated. On basis of the biological-chemical-cycle coupling mechanism, the kinetics of biomimetic catalytic oxidation of toluene has been studied. And the corresponding kinetics mathematic model of toluene oxidation is developed firstly. Then by use of the kinetics model the experiment phenomena and the law of toluene oxidation have been analyzed quantitatively. According to the kinetics model several possible reactor models are established to optimize the oxidation reactor and reaction conditions for toluene oxidation in presence of metalloporphyrin. Finally the some chemical engineering problems of industrial synthesis of porphyrin are solved successfully. First industrial-scale synthesis of T(p-C1)PPH2and (T(p-C1)PPFe)2O has been carried out successfully in the plant designed by ourselves to produce porphyrin catalyst, and the process of industrial synthesis of cobaltporphyrin has been developed too. The main research works and results are as follows:
1. The liquid-phase catalytic aerobic oxidation of toluene by metalloporphyrin is studied in a series of three stirred tank reactors. The effects of operation mode(including batch and continuous operation), catalyst and optimal catalyst concentration on the oxidation process are examined. The conversion of toluene and the selectivity to benzaldehyde and benzyl alcohol are chosen as the evaluating index. The research results are:the best catalyst is (T(p-C1)PPFe)2O and its concentration is2ppm.
2. In order to determine the control step of toluene oxidation process accurately an improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperatures and pressures is used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin.
3. Under oxygen transfer limitations and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin is studied. The effect of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene are systematically investigated. The results show that the toluene conversion under the oxygen transfer limitations is lower by2～4%(mol) than that under kinetic control under same oxidation conditions. And the total selectivity of benzaldehyde and benzyl alcohol under the oxygen transfer limitations is lower by8～10%(mol) than that under kinetic control with the same conversion of toluene. The rate of oxygen transfer doesn't influence toluene conversion and the selectivity of benzaldehyde and benzyl alcohol under the kinetics control conditions, and toluene oxidation is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrin.
4. On basis of the biological-chemical-cycle coupling mechanism, the kinetics of biomimetic catalytic oxidation of toluene has been studied. And the corresponding kinetics mathematic model of toluene oxidation is developed firstly. Then by use of the kinetics model the physical meaning of model parameters are analyzed in detail according to the oxidation process of toluene.
5. The16kinetics model parameters are determined in a nonlinear optimization, minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a batch oxidation reactor where the gas and liquid phases are well mixed, and the standard deviation of the simulated and experimental data is less than5%. The biological-chemical-cycle coupling process of toluene oxidation is explained quantitatively, the reason of high selectivity to benzaldehyde and benzyl alcohol during the toluene oxidation in presence of metalloporphrin is explained successfully according the relation of reaction activation energy.
6. According to the kinetics model several possible reactor model are established to optimize the oxidation reactor and reaction conditions for toluene oxidation in presence of metalloporphyrin. The optimal results are:the conversion of toluene and the selectivity to benzaldehyde and benzyl alcohol is chosen as the evaluating index, the three continuous stirred tank reactors in series is appropriate for toluene oxidation; the optimal reaction temperature is463K,468K,473K each and average residence time of each is39min, 30min,21min; Under these reaction conditions the toluene conversion is10.07%(mol) and the selectivity to benzaldehyde and benzyl alcohol is47.57%(mol). By using the continuous mathematic reaction model for toluene oxidation with biomimetic catalyst, the maximal relative deviation between the experimental and calculated data is less than7.97%.The average relative deviation between the experimental and calculated data equals to3.69%.The reactor model predicted data for toluene oxidation systems agree with the experimental determined results satisfactorily.
7. The plant to produce porphyrin catalyst has been designed and installed. The process of industrial synthesis of T(p-C1)PPH2has been optimized.The results are:the yield of T(p-C1)PPH2can reach31.90%, while the yield is only about20%in laboratory; According to kinetics of synthesis of cobaltporphyrin, a batch reaction model for synthesis of cobaltporphyrin has been established, and by use of this model the optimal synthesis conditions have been obtained successfully. Under these optimal conditions the yield of the industrial synthesis of cobaltporphrin can reach98.00%; Final the effects of reaction temperature and PH on the yield for industrial synthesis of (T(p-C1)PPFe)2O has been investigated. And the yield for industrial synthesis of (T(p-C1)PPFe)2O is more than98.00%.
引文
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