ZrO2基复合金属氧化物催化剂上CO2温和氧化乙苯制苯乙烯

doi:10.1016/S1872-2067(15)60901-9

摘要/Abstract

摘要：

苯乙烯(SM)是聚合物化学中最重要的单体之一,由其生产的聚合物产品(如PS,SBR和ABS等)具有独特的性能,因而SM的需求逐年增加.乙苯(EB)催化脱氢工艺提供了90%的SM需求,该过程在K促进的氧化铁催化剂上于600-650℃进行.这是一个吸热且体积增大的反应,因此需要绝热反应器和大量的过热过饱和蒸汽以提供热量和降低反应分压,从而有利于反应平衡向SM方向移动,也可避免或消除积碳.同时,也造成大量潜热被浪费;热点也降低了整个反应活性和催化剂寿命.在蒸汽中加入空气或富氧空气,使得副产H₂与O₂反应,产生的热量可供随后乙苯脱氢反应,同时H₂的移除也有利于提高EB单程转化率,并保持高的SM选择性.但是,该过程需要2个催化剂,反应器的设计和催化剂的装填比较复杂,且存在爆炸的危险.因此,人们尝试了多种氧化剂和新型的催化剂.最近也有人提出软氧化剂的概念.这为开发新催化体系提供了可能.
相对于O₂,CO₂的氧化性很弱,但可用作温和氧化剂去除脱氢单元中副产的H₂,降低了反应温度,且不影响反应活性和选择性;同时,具有较大的经济性和环保性,在工业上也是切实可行的.除了负载型的碱金属促进的氧化铁催化剂外,各种金属或金属氧化物也用于催化CO₂氧化EB脱氢反应中,如Fe,Cr,V和La的氧化物为活性金属,碳材料、MgO、SiO₂、Al₂O₃、Ga₂O₃、ZrO₂、TiO₂、水滑石类化合物及分子筛为载体.Park课题组研究了Fe,V和Cr基催化剂,即设计氧化还原的催化剂表面以解离CO₂,产生的O用于逆水汽反应.其中以Al₂O₃负载的V和V-Sb氧化物催化剂性能最为突出;但存在积碳失活和V物种的深度还原等问题.为了进一步提高催化剂性能,该课题组开发了多种ZrO₂基复合氧化物催化剂,包括MnO₂-ZrO₂, TiO₂-ZrO₂, CeO₂-ZrO₂和SnO₂-ZrO₂.这些催化剂具有酸碱特性,在反应中表现出较高的催化性能.因此,本文简要总结了用于CO₂氧化EB脱氢反应的ZrO₂基催化剂最新研究进展.
研究发现,在CO₂氧化EB脱氢制SM反应中,CO₂在提高催化剂活性和稳定性方面起着非常重要的作用,可被定义为软氧化剂:氧化催化剂表面以保持其表面氧含量,移除催化剂表面产生的积碳和副产物H₂,为反应体系提供较高的热容以克服反应平衡限制,从而达到较高的转化率.ZrO₂基复合金属氧化物是具有改善的织构特性的纳米粒子,且具有酸碱两性和氧化还原性能.改性可提高催化体系的热稳定性和活性.其中CeO₂-V₂O₅/TiO₂-ZrO₂催化剂具有恰当的氧化还原性和酸碱两性,二者协同作用,因而催化性能最佳.氧化还原稳定剂Sb的添加进一步提高了其催化性能.碱金属和碱土金属可优化其酸碱性,增加比表面积,从而提高反应活性和选择性以及CO₂转化率.继续加强抑制积碳和促进CO₂活化方面的研究,可有望进一步提高单程转化率(75%以上)、选择性(98%)和CO₂转化率(30%).
总之,CO₂氧化EB脱氢制SM是一个高度经济性和环境友好的新过程,在未来有望满足SM日益增长的需求.另外,该过程的开发可减少CO₂排放,其副产的CO还可用于多种化工过程.然而,该过程仍面临诸多挑战:如何抑制积碳,单程转化率和催化剂寿命有待进一步提高.这些挑战也给我们未来的研究提供了方向.深入理解反应机理、积碳机理和CO₂的活化过程也有利于我们开发出更适合工业应用的催化剂.

关键词: 氧化脱氢, CO₂活化, ZrO₂基复合氧化物, 酸碱性, 氧化还原性

Abstract:

ZrO₂-based mixed metal oxide catalysts for the industrially important dehydrogenation process of ethylbenzene to styrene monomer have been explored by our group for the past 20 years. These efforts were subjected to the activation of CO₂ over mixed metal oxide catalysts and resulted in several promising benefits to the dehydrogenation processes, such as stabilized conversion and selectivity, suppressed coke formation and commercially-acceptable longevity. In this review, we summarize the most recent developments on ZrO₂-based mixed metal oxide catalysts, including the further optimization of sol-gel process in the synthesis of catalysts, rationalizing acid-base properties by doping, co-operative properties between redox and acid-base active sites and additional promoters towards the effective improvement of the longevity of catalysts.

Key words: Oxidative dehydrogenation, Carbon dioxide activation, Zirconia-based mixed oxide, Acid-base properties, Redox properties

Nanzhe Jiang, Abhishek Burri, Sang-Eon Park. ZrO₂基复合金属氧化物催化剂上CO₂温和氧化乙苯制苯乙烯[J]. 催化学报, 2016, 37(1): 3-15.

Nanzhe Jiang, Abhishek Burri, Sang-Eon Park. Ethylbenzene to styrene over ZrO₂-based mixed metal oxide catalysts with CO₂ as soft oxidant[J]. Chinese Journal of Catalysis, 2016, 37(1): 3-15.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(15)60901-9

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ZrO₂基复合金属氧化物催化剂上CO₂温和氧化乙苯制苯乙烯

Ethylbenzene to styrene over ZrO₂-based mixed metal oxide catalysts with CO₂ as soft oxidant

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