Hydrogenation of dinitriles on Raney-type Ni catalysts: kinetic and mechanistic aspects |
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| Authors: | Bram W Hoffer Jacob A Moulijn |
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| Affiliation: | 1. Catalysis Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands;1. Boreskov Institute of Catalysis, pr. Lavrentieva 5, 630090, Novosibirsk, Russia;2. Novosibirsk State University, Pirogova 2, 630090, Novosibirsk, Russia;3. Novosibirsk Institute of Organic Chemistry, pr. Lavrentieva 9, 630090, Novosibirsk, Russia;4. Universidad Nacional Autónoma de México, Centro de Nanociencias y Nanotecnología, km. 107 carretera Tijuana a Ensenada, C.P. 22860, Ensenada, Baja California, Mexico;5. Process Chemistry Centre, Åbo Akademi University, FI-20500, Turku, Åbo, Finland;1. CSA Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China;2. University of Chinese Academy of Sciences, Beijing 100049, China;3. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;4. Dalian National Laboratory for Clean Energy, Dalian 116023, China;1. Institut de chimie des milieux et matériaux de Poitiers (IC2MP) CNRS: UMR 7285–Université de Poitiers, France;2. Laboratory of Catalysis and Corrosion of Materials, University of El Jadida, Morocco;3. Dept of Chemical Engineering, University of South Carolina, Columbia, USA;1. State Key Laboratory of Advanced Special Steel, School of Materials Science and Engineering, Shanghai University, Shanghai, 200072, China;2. Technology Research Institute of Shanghai Huayi Group, Shanghai, 200241, China |
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| Abstract: | The mechanism of the hydrogenation of aliphatic C4–C6 dinitriles (succinonitrile, glutaronitrile, and adiponitrile) over Raney-type Ni catalysts was investigated in a fed-batch autoclave at 350 K and 5.0 MPa. The results are interpreted based on the strength of adsorption, the interaction with the solvent and intramolecular interactions. The kinetics of the hydrogenation of aliphatic dinitriles is highly dependent on the hydrocarbon chain length. Short dinitriles like succinonitrile adsorb stronger on the catalyst surface than longer dinitriles like adiponitrile. The yield of the intermediate aminonitriles decreases with increasing hydrocarbon chain length, due to the enhanced competitiveness of dinitrile and aminonitrile for the same active sites. It is proposed that the reactivity of dinitriles and aminonitriles is caused by difference in solvent interaction. It is remarkable that the stronger the adsorption, the higher the reactivity. The reactivity decreases in the order: succinonitrile > glutaronitrile > adiponitrile. In contrast, the reaction rate of the aminonitriles is fairly independent of the hydrocarbon chain length. The formation of undesired secondary amines in the form of cyclic compounds is under kinetic control and increases with decreasing chain length. It is found that adiponitrile can be very selectively hydrogenated to primary diamines. Promoting Raney-type Ni catalysts with traces of Mo, Cr or Fe enhances the performance in the hydrogenation of dinitriles. This gives the best opportunity for process improvement towards the desired primary amines. |
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