Festa Giovanni, Contaldo Palma, Martino Marco, Meloni Eugenio, Palma Vincenzo
Department of Industrial Engineering, University of Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, SA, Italy.
Ind Eng Chem Res. 2023 Oct 9;62(41):16622-16637. doi: 10.1021/acs.iecr.3c01076. eCollection 2023 Oct 18.
The propylene production processes currently used in the petrochemical industry (fluid catalytic cracking and steam cracking of naphtha and light diesel) are unable to meet the increase of propylene demand for industrial applications. For this reason, alternative processes for propylene production have been investigated, and among the others, the propane dehydrogenation (PDH) process, allowing the production of propylene as a main product, has been industrially implemented (e.g., Catofin and Oleflex processes). The main drawback of such processes is closely linked to the high temperature required to reach a sustainable propane conversion that affects catalyst stability due to coke formation on the catalyst surface. Accordingly, the periodic regeneration of the catalytic bed is required. In this work, the performance in the PDH reaction of different Sn-Pt catalysts, prepared starting by alumina- and hydrotalcite-based supports, is investigated in terms of propane conversion and selectivity to propylene in order to identify a more stable catalyst than the commercial ones. The experimental tests evidenced that the best performance was obtained using the catalyst prepared on commercial pellets of hydrotalcite PURALOX MG70. This catalyst has shown, under pressure conditions of 1 and 5 bar (in order to evaluate the potential future application in integrated membrane reactors), propane conversion values close to the thermodynamic equilibrium ones in all of the investigated temperature ranges (500-600 °C) and the selectivity was always higher than 95%. So, this catalyst was also tested in a stability run, performed at 500 °C and 5 bar: the results highlighted the loss of only 12% in the propane conversion with no changes in the selectivity to propylene. Properly designed experimental tests have also been performed in order to evaluate the kinetic parameters, and the developed mathematical model has been optimized to effectively describe the system behavior and the catalyst deactivation.
目前石油化工行业中使用的丙烯生产工艺(石脑油和轻柴油的流化催化裂化和蒸汽裂解)无法满足工业应用中对丙烯需求的增长。因此,人们研究了丙烯生产的替代工艺,其中丙烷脱氢(PDH)工艺可将丙烯作为主要产品进行生产,已在工业上得到应用(例如,Catofin和Oleflex工艺)。此类工艺的主要缺点与实现可持续丙烷转化率所需的高温密切相关,由于催化剂表面形成焦炭,这会影响催化剂的稳定性。因此,需要对催化床进行定期再生。在这项工作中,研究了以氧化铝和水滑石为载体制备的不同Sn-Pt催化剂在PDH反应中的性能,考察了丙烷转化率和对丙烯的选择性,以确定一种比市售催化剂更稳定的催化剂。实验测试表明,使用在水滑石PURALOX MG70商业颗粒上制备的催化剂可获得最佳性能。在1和5巴的压力条件下(为了评估其在集成膜反应器中的潜在未来应用),该催化剂在所有研究的温度范围(500-600℃)内的丙烷转化率值接近热力学平衡值,且选择性始终高于95%。因此,还在500℃和5巴下对该催化剂进行了稳定性测试:结果表明,丙烷转化率仅损失12%,而对丙烯的选择性没有变化。还进行了经过适当设计的实验测试以评估动力学参数,并对所建立的数学模型进行了优化,以有效描述系统行为和催化剂失活情况。