丁烷选择氧化制顺酐VPO催化剂再氧化性能的研究
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摘要
VPO催化剂上丁烷选择氧化制顺酐是迄今唯一已经工业化的、非均相催化、低碳烷烃选择氧化制含氧化合物的反应，以丁烷选择氧化制顺酐体系为模型反应，采用热分析仪，固定床微型反应器、气相色谱、在线质谱等手段，对三种VPO催化剂，进行催化剂氧化再生动力学行为和定态反应特性研究，从中筛选出最适于非定态操作的催化剂，然后仔细研究其再氧化性能，优选人为非定态操作反应条件。
主要工作包括：
首先，建立了一种简单实用的气相色谱分析方法，改建一套适合定态反应性能评价的微型固定床反应器实验装置，对三种催化剂进行定态反应性能评价和比较。
其次，利用热分析仪，通过程序升温氧化(TPO)实验对催化剂氧化再生行为进行研究，结合定态性能评价结果，从中筛选出一种最适宜于人为非定态反应的催化剂。
第三，导出了VPO-1催化剂再氧化速率方程并用实验进行了判识，结果表明，氧化再生过程遵循相边界反应控制的收缩核模型，
北京化工大学硕士学位论文
催化剂体相晶格氧扩散速率相对较快，对反应速率影响较小。
最后，通过进料组成周期性调变热分析实验和质谱在线动态响
应检测，得到了催化剂质量和产物气组成周期性变化曲线，结果表
明，REDOX循环是稳定的。
The partial oxidation of n-butane to Maleic Anhydride (MA) over vanadium phosphorus oxide (VPO) catalyst is still the only heterogeneously catalyzed, alkane-selective oxidation reaction in commercial use.
Three kinds of VPO catalysts, used to the model reaction system, n-butane oxidation to MA were investigated. By the means of thermogravimetric unit, fixed bed micro-reactor, on-line chromatographic and mass spectroscopy, oxidation regeneration kinetics and the performance of steady-state reaction were probed. The best catalyst suitable to forced unsteady-state reaction was distinguished.
At first, a simple, and accurate GC analysis method and the method for processing experimental data were established for n-butane selective oxidation to MA. An experimental set-up was built for investigating the steady-state operation of fixed bed reactor. Under steady-state conditions, the performances of three kinds of the VPO catalysts were evaluated and compared each other.
Secondly, the thermal oxidation regeneration process and its reaction kinetics were investigated by temperature-programmed-oxidation (TPO). The best catalyst suitable to forced unsteady-state reaction was distinguished, combining steady-state performance.
Thirdly, re-oxidation rate equation was deduced and identified. The results show that the re-oxidation process of the catalyst obeys the contracted core model controlled by phase border, and the rate-controlling step is chemical reaction. A model of oxidation regeneration process for VPO catalyst is developed for simulation and prediction purposes.
Finally, using TGA unit and on-line mass spectroscopy (MS) transient measurement in fixed bed micro-reactor, the modulation of feed composition transient response experiments were completed and the stability of REDOX cycle was also examined.
主要工作包括：
首先，建立了一种简单实用的气相色谱分析方法，改建一套适合定态反应性能评价的微型固定床反应器实验装置，对三种催化剂进行定态反应性能评价和比较。
其次，利用热分析仪，通过程序升温氧化(TPO)实验对催化剂氧化再生行为进行研究，结合定态性能评价结果，从中筛选出一种最适宜于人为非定态反应的催化剂。
第三，导出了VPO-1催化剂再氧化速率方程并用实验进行了判识，结果表明，氧化再生过程遵循相边界反应控制的收缩核模型，
北京化工大学硕士学位论文
催化剂体相晶格氧扩散速率相对较快，对反应速率影响较小。
最后，通过进料组成周期性调变热分析实验和质谱在线动态响
应检测，得到了催化剂质量和产物气组成周期性变化曲线，结果表
明，REDOX循环是稳定的。
The partial oxidation of n-butane to Maleic Anhydride (MA) over vanadium phosphorus oxide (VPO) catalyst is still the only heterogeneously catalyzed, alkane-selective oxidation reaction in commercial use.
Three kinds of VPO catalysts, used to the model reaction system, n-butane oxidation to MA were investigated. By the means of thermogravimetric unit, fixed bed micro-reactor, on-line chromatographic and mass spectroscopy, oxidation regeneration kinetics and the performance of steady-state reaction were probed. The best catalyst suitable to forced unsteady-state reaction was distinguished.
At first, a simple, and accurate GC analysis method and the method for processing experimental data were established for n-butane selective oxidation to MA. An experimental set-up was built for investigating the steady-state operation of fixed bed reactor. Under steady-state conditions, the performances of three kinds of the VPO catalysts were evaluated and compared each other.
Secondly, the thermal oxidation regeneration process and its reaction kinetics were investigated by temperature-programmed-oxidation (TPO). The best catalyst suitable to forced unsteady-state reaction was distinguished, combining steady-state performance.
Thirdly, re-oxidation rate equation was deduced and identified. The results show that the re-oxidation process of the catalyst obeys the contracted core model controlled by phase border, and the rate-controlling step is chemical reaction. A model of oxidation regeneration process for VPO catalyst is developed for simulation and prediction purposes.
Finally, using TGA unit and on-line mass spectroscopy (MS) transient measurement in fixed bed micro-reactor, the modulation of feed composition transient response experiments were completed and the stability of REDOX cycle was also examined.
引文
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