氧化锰催化剂在环己烷无溶剂选择性氧化反应中的活性:焙烧温度的影响

doi:10.1016/S1872-2067(15)60983-4

催化学报 ›› 2016, Vol. 37 ›› Issue (1): 184-192.DOI: 10.1016/S1872-2067(15)60983-4

氧化锰催化剂在环己烷无溶剂选择性氧化反应中的活性:焙烧温度的影响

吴明周, 詹望成, 郭耘, 王筠松, 郭杨龙, 龚学庆, 王丽, 卢冠忠

华东理工大学结构可控先进功能材料及其制备教育部重点实验室和工业催化研究所, 上海200237

收稿日期:2015-08-09 修回日期:2015-09-22 出版日期:2015-12-26 发布日期:2015-12-26
通讯作者: 卢冠忠, 詹望成
作者简介:卢冠忠, 詹望成
基金资助:
国家重点基础研究发展计划(2010CB732300); 国家自然科学基金(21103048).

Solvent-free selective oxidation of cyclohexane with molecular oxygen over manganese oxides: Effect of the calcination temperature

Mingzhou Wu, Wangcheng Zhan, Yun Guo, Yunsong Wang, Yanglong Guo, Xueqing Gong, Li Wang, Guanzhong Lu

Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China

Received:2015-08-09 Revised:2015-09-22 Online:2015-12-26 Published:2015-12-26
Supported by:
This work was supported by the National Basic Research Program of China (973 Program, 2010CB732300) and the National Natural Science Foundation of China (21103048).

摘要/Abstract

摘要：

环己醇和环己酮俗称KA油,是用于制备尼龙材料的己二酸和己内酰胺的重要中间体.工业上制取环己醇和环己酮的方法主要为苯酚加氢法、环己烯水合法和环己烷氧化法,其中环己烷氧化法的应用最为普遍,包括硼酸氧化法、过氧化物氧化法和钴盐催化氧化法三种路线.为获得适宜的环己醇和环己酮选择性,工业上环己烷氧化单程转化率通常控制在5.0%以下,从而使得产物选择性在80%以上.因此,现有环己烷氧化法生产KA油的最大挑战是如何同时获得高环己烷转化率和高KA油选择性.迄今,已有多种催化剂被尝试用于环己烷氧化反应,包括金属卟啉、金属氧化物、分子筛、碳纳米管和金属-有机骨架材料等.由于均相催化剂无法从环己烷氧化反应体系中分离出来,导致催化剂不能重复利用,因此多相催化剂的研究更受青睐.另外,由于采用氧气为氧化剂时具有环境友好和更高的原子经济性,因此氧气选择性氧化环己烷反应已逐渐成为环己烷氧化法制KA油中最具挑战性的研究.目前,氧气为氧化剂时的环己烷转化率通常低于过氧化氢和叔丁基过氧化氢等为氧化剂时的转化率,其关键在于适用于固(催化剂)液(环己烷)气(氧化剂)反应体系的高性能催化剂.本课题组前期研究了系列金属掺杂分子筛(Ce/AlPO-5,Ce-MCM-41/48和Mg-Cu/SBA-15等)对氧气催化氧化环己烷的反应性能,发现无论是稀土还是过渡金属掺杂,通过影响环己烷氧化反应的自由基产生和反应历程,可显著提高环己烷转化率或者KA油的选择性. 基于此,本文选择原料易得、成本较低和氧化能力强的氧化锰(MnO_x)作为具有强氧化能力的过渡金属氧化物的代表,深入研究了MnO_x的焙烧温度对其结构和选择性氧化环己烷反应性能的影响,同时研究了反应条件对催化剂性能的影响.
结果表明,400℃焙烧制得的催化剂(MnO_x-400)比350,450和500℃焙烧制得的催化剂具有更高的活性. 在最佳反应条件(140oC,O₂起始压力0.5MPa,反应4h)下,使用20mgMnO_x-400可使环己烷转化率达8.0%,KA油得率为5.0%.过高的反应温度、过长的反应时间和过高的反应压力都会导致产物被过度氧化,KA油选择性降低.另外,该催化剂重复使用10次,其活性没有明显下降,显示出了很好的稳定性.表征测试结果表明,MnO_x催化剂在不同温度焙烧后形成了不同的结晶形态: 焙烧温度小于500oC时,催化剂主要组成为Mn₃O₄和Mn₅O₈,500oC时主要为Mn₃O₄,Mn₅O₈和Mn₂O₃.而且随着焙烧温度升高,MnO_x催化剂的比表面积逐渐降低.相比于350oC焙烧制得的催化剂,MnO_x-400催化剂具有更好的结晶形态,这可能是造成其活性较好的原因.而相比于MnO_x-400,500oC焙烧制得的催化剂表面Mn⁴⁺含量和表面吸附氧含量较低,使其吸附和活化氧能力降低,从而导致催化剂活性低于MnO_x-400;但是吸附和活化氧能力的降低有利于减缓反应产物的深度氧化,因而KA油的选择性增加.

关键词: 氧化锰, 环己烷选择氧化, 氧气, 焙烧温度, 无溶剂反应

Abstract:

The effects of calcination temperature on the physicochemical properties of manganese oxide catalysts prepared by a precipitation method were assessed by X-ray diffraction, N₂ adsorption-desorption, X-ray photoelectron spectroscopy, H₂ temperature-programmed reduction, O₂ temperature-programmed desorption, and thermogravimetry-differential analysis. The catalytic performance of each of these materials during the selective oxidation of cyclohexane with oxygen in a solvent-free system was subsequently examined. It was found that the MnO_x-500 catalyst, calcined at 500 ℃, consisted of a Mn₂O₃ phase in addition to Mn₅O₈ and Mn₃O₄ phases and possessed a low surface area. Unlike MnO_x-500, the MnO_x-400 catalyst prepared at 400 ℃ was composed solely of Mn₃O₄ and Mn₅O₈ and had a higher surface area. The pronounced catalytic activity of this latter material for the oxidation of cyclohexene was determined to result from numerous factors, including a higher concentration of surface adsorbed oxygen, greater quantities of the surface Mn⁴⁺ ions that promote oxygen mobility and the extent of O₂ adsorption and reducibility on the catalyst. The effects of various reaction conditions on the activity of the MnO_x-400 during the oxidation of cyclohexane were also evaluated, such as the reaction temperature, reaction time, and initial oxygen pressure. Following a 4 h reaction at an initial O₂ pressure of 0.5 MPa and 140 ℃, an 8.0% cyclohexane conversion and 5.0% yield of cyclohexanol and cyclohexanone were achieved over the MnO_x-400 catalyst. In contrast, employing MnO_x-500 resulted in a 6.1% conversion of cyclohexane and 75% selectivity for cyclohexanol and cyclohexanone. After being recycled through 10 replicate uses, the catalytic activity of the MnO_x-400 catalyst was unchanged, demonstrating its good stability.

Key words: Manganese oxide catalyst, Selective oxidation of cyclohexane, Oxygen, Calcination temperature, Solvent-free reaction

吴明周, 詹望成, 郭耘, 王筠松, 郭杨龙, 龚学庆, 王丽, 卢冠忠. 氧化锰催化剂在环己烷无溶剂选择性氧化反应中的活性:焙烧温度的影响[J]. 催化学报, 2016, 37(1): 184-192.

Mingzhou Wu, Wangcheng Zhan, Yun Guo, Yunsong Wang, Yanglong Guo, Xueqing Gong, Li Wang, Guanzhong Lu. Solvent-free selective oxidation of cyclohexane with molecular oxygen over manganese oxides: Effect of the calcination temperature[J]. Chinese Journal of Catalysis, 2016, 37(1): 184-192.

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氧化锰催化剂在环己烷无溶剂选择性氧化反应中的活性:焙烧温度的影响

Solvent-free selective oxidation of cyclohexane with molecular oxygen over manganese oxides: Effect of the calcination temperature

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