姜淼, 杜虹, 王国庆, 严丽, 丁云杰. Co-PPh3@POPs多相催化剂氢甲酰化反应研究[J]. 煤炭学报, 2020, 45(4). DOI: 10.13225/j.cnki.jccs.YH20.0177
引用本文: 姜淼, 杜虹, 王国庆, 严丽, 丁云杰. Co-PPh3@POPs多相催化剂氢甲酰化反应研究[J]. 煤炭学报, 2020, 45(4). DOI: 10.13225/j.cnki.jccs.YH20.0177
JIANG Miao, DU Hong, WANG Guoqing, YAN Li, DING Yunjie. Co-PPh3@ POPs heterogeneous catalysts for hydroformylation of olefins[J]. Journal of China Coal Society, 2020, 45(4). DOI: 10.13225/j.cnki.jccs.YH20.0177
Citation: JIANG Miao, DU Hong, WANG Guoqing, YAN Li, DING Yunjie. Co-PPh3@ POPs heterogeneous catalysts for hydroformylation of olefins[J]. Journal of China Coal Society, 2020, 45(4). DOI: 10.13225/j.cnki.jccs.YH20.0177

Co-PPh3@POPs多相催化剂氢甲酰化反应研究

Co-PPh3@ POPs heterogeneous catalysts for hydroformylation of olefins

  • 摘要: 氢甲酰化反应是过渡金属羰基化合物催化下的烯烃与合成气生成比原料烯烃高一个碳的醛或醇的反应,全世界通过氢甲酰化反应制备醛或醇的产量可以达到1 200万t/a。均相催化具有较高的催化活性和温和的反应条件,但催化剂同反应物料的分离问题,阻碍了其大规模工业化应用。多相催化体系中催化剂与反应物料容易分离,存在反应活性或选择性较低等问题。均相固载化兼顾了均相催化优异的反应活性和多相催化易于分离的优点,成为氢甲酰化领域的研究热点。Rh是氢甲酰化反应中最活泼的元素,Co的活性相对较低,但其仍具有较大的工业价值。由于贵金属Rh的资源稀缺以及价格昂贵严重影响了氢甲酰化反应过程的经济性,因此,考虑采用金属Co代替金属Rh作为催化剂的活性组分,应用于烯烃的多相氢甲酰化反应。制备了PPh3@POPs担载Co基多相催化剂(Co-PPh3@POPs),系统考察了反应溶剂、金属Co前驱物、金属Co负载量、反应时间等因素对Co-PPh3@POPs催化剂氢甲酰化反应性能的影响。当选取反应溶剂为甲苯,金属Co前驱物为Co(OAc)2,Co负载量为10%时,Co-PPh3@POPs催化剂表现出良好的氢甲酰化反应性能,且反应活性明显优于Co@SiO2和Co@SBA-15催化剂。表征结果显示,Co-PPh3@POPs催化剂具有高的热稳定性、大比表面积和多级孔道结构,较优的催化性能归因于活性组分Co物种可高分散于具有大比表面积和多级孔道结构的含膦聚合物PPh3@POPs载体上。

     

    Abstract: Hydroformylation is widely used to produce aldehydes or alcohols by the addition of syngas to olefins,which is catalyzed by transition metal complexes. Although homogeneous catalysts exhibit an excellent activity under mild re- action conditions,its industrial application on a large scale is hindered by the separation of the catalyst from the prod- uct. The prominent advantage of a heterogeneous catalyst is its easy separation from the product in contrast to a homo- geneous catalyst. However,heterogeneous catalysts suffer the problem of low activity or selectivity. Extensive research has been devoted to developing heterogenized homogeneous catalysts which combine the practical advantages of heterogeneous catalysts with the high efficiency of homogeneous catalysts. Rh is the most catalytic active for the hydroformy- lation of olefins. Although the catalytic active for Co is relatively low,the application of Co for hydroformylation has some industrial values. Noble metal Rh is the scarce resource and high cost,therefore,this paper studied the Co based heterogeneous hydroformylation of olefins. The Co-PPh3 @ POPs heterogeneous catalyst was prepared for the hydro- formylation of olefins. The influence of solvent,Co precursors,Co loading and reaction time on the activity of hydro- formylation over the Co-PPh3 @ POPs catalysts were investigated in detail. Toluene solvent,Co( OAc)2 and 10% Co loading were the optimal conditions for Co-PPh3 @ POPs catalysts. It showed higher activity than other inorganic carri- ers supported Co based heterogeneous catalysts such as Co@ SiO2 and Co@ SBA-15. Thermogravimetry,N2 adsorption, scanning electron microscopy and transmission electron microscopy indicated the Co-PPh3 @ POPs catalyst featured su- perior thermal stability,high surface areas,hierarchical porosity and highly uniform dispersed Co species.

     

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