124-09-4Relevant articles and documents
Supported Ni catalyst for liquid phase hydrogenation of adiponitrile to 6-Aminocapronitrile and hexamethyenediamine
Wang, Chengqiang,Jia, Zekun,Zhen, Bin,Han, Minghan
, (2018)
Supported Ni catalysts prepared under different conditions, for liquid phase hydrogenation of adiponitrile (ADN) to 6-aminocapronitrile (ACN) and hexamethyenediamine (HMD), were investigated. The highly reactive imine intermediate can form condensation byproducts with primary amine products (ACN and HMD), which decreased the yield coefficient of primary amines. The catalysts support, condition of catalyst preparation and dosage of additive were studied to improve the yield. A highly dispersed Ni/SiO2 catalyst prepared by the direct reduction of Ni(NO3)2/SiO2 suppressed the condensation reactions by promoting the hydrogenation of adsorbed imines, and it gave the improved hydrogenation activity of 0.63 mol·kgcat?1·min?1 and primary amine selectivity of 94% when NaOH was added into the reactor.
Industrial preparation method of hexamethylenediamine
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Paragraph 0029; 0031-0033; 0035-0037; 0039-0040; 0044-0045, (2021/06/13)
The invention discloses an industrial preparation method of hexamethylenediamine, wherein the industrial preparation method comprises the following steps: 1) dissolving cyclohexene in a first organic solvent, carrying out electrocatalytic oxidation reaction in a reaction kettle, carrying out constant potential electrolysis to obtain a reaction solution, and carrying out reduced pressure distillation to obtain adipic dialdehyde; and 2) dissolving adipic dialdehyde in a second organic solvent, introducing ammonia gas and hydrogen, and carrying out reductive amination reaction under the action of a supported nickel catalyst to obtain the hexamethylenediamine. The reaction adopts an electrocatalytic oxidation mode, and the selectivity is controlled by utilizing electrode potential, so that the reaction is more accurate and sufficient, the product conversion rate is improved, and the product is easy to separate, clean and environment-friendly; according to the method, hexamethylenediamine can be prepared through rectification operation, the product conversion rate of the method reaches 98.70%, the total yield reaches 98.02%, the purity reaches 95.14%-98.13%, the requirements of industrial production are met, and the method has good application prospects in industry; in addition, raw materials and auxiliary materials are simple and easy to obtain, the price is low, the input cost is low, and the construction scale is not limited.
Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
, p. 3943 - 3957 (2021/04/12)
The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.