Amination of cyclohexanone and cyclohexanol/cyclohexanone in the presence of ammonia and hydrogen using copper or a group VIII metal supported on a carrier as the catalyst

Becker, Jürgen; Niederer, John P.M.; Keller, Martin; Hölderich, Wolfgang F.

doi:10.1016/s0926-860x(99)00482-2

Cited by 46 publications

(33 citation statements)

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“…According to the reaction mechanism (see Scheme 3), a decrease in the amount of NH 3 should increase, in fact, the contribution of step (2.1) leading to the formation of imine 4, whose hydrogenation gives dicyclohexylamine (3). The decrease in the conversion with an increase in the ammonia amount can be due to a decrease in the rate of hydrogenation step (2.2) because of the competitive adsorption of NH 3 and primary amine on the catalyst surface.…”

Section: Methodsmentioning

confidence: 99%

“…The main methods for its production are the hydrogenation of aniline and reductive amination (hydroamination) of cyclohexanone. [1][2][3][4] Carbonyl compounds are hydroaminated by ammonia and hydrogen in the presence of hydrogenation catalysts, among which the catalysts based on nickel and platinum group metals are used most frequently. 4 This reaction was first carried out in the liquid phase at room temperature and atmospheric pressure on the nickel and copper cata lysts.…”

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Liquid-phase hydroamination of cyclohexanone

et al. 2010

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Activity and selectivity of supported Ni, Pt, and Pd catalysts were studied in the liquid phase reductive amination of cyclohexanone at temperatures ranging from 100 to 150 °C. The catalyst 20% Ni/SiO 2 is most active and selective providing a maximum yield of cyclohexyl amine. The influence of the reaction conditions on the parameters of the catalytic process was studied. A detailed analysis of the reaction products was carried out using 13 C NMR spectrosco py and gas chromatography coupled with mass spectrometry (GC MS). This made it possible to refine the reaction mechanism and to identify a new by product earlier unknown in the literature.The annual worldwide demand for cyclohexylamine stands at several thousands tonnes 1 and, hence, it is an important product of modern large scale chemistry. The main methods for its production are the hydrogenation of aniline and reductive amination (hydroamination) of cyclohexanone. 1-4Carbonyl compounds are hydroaminated by ammonia and hydrogen in the presence of hydrogenation catalysts, among which the catalysts based on nickel and platinum group metals are used most frequently. 4 This reaction was first carried out in the liquid phase at room temperature and atmospheric pressure on the nickel and copper cata lysts. 5 Higher yields of amines were obtained by using Raney nickel at elevated hydrogen pressure (20-150 atm) and 40-150 °С (see Ref. 6). Further investigations showed that this reaction can be carried out in the liquid or gas phase in the presence of massive metal and supported het erogeneous hydrogenation catalysts based on transition metals Ni, Co, and Fe or platinum group metals. 3,4,7-9The synthesis of primary amines is complicated by the formation of secondary and tertiary amines. The product distribution can depend on the catalyst nature, the ratio of a carbonyl compound and ammonia, and other reaction conditions. For instance, the liquid phase hydroamina tion of cyclohexanone by ammonia in the presence of the nickel catalysts leads to predominant formation of cyclo hexylamine, whereas secondary amine is the major prod uct in the case of the platinum catalysts. 4,7,10,11 The nick el catalysts are considered to be most available and effi cient for cyclohexylamine production. 4,7According to the commonly accepted mechanism of ketone hydroamination, 2,4,7,8,12,13 at the first non cata lytic step ammonia reacts with ketone to form intermedi ate primary imine, which is further hydrogenated on the catalyst to form primary amine. In turn, the primary amine can react with ketone to form secondary imine, whose hydrogenation gives secondary amine. Such side reactions as the hydrogenation of ketone and its aldol condensation can also occur during hydroamination. 7, 8 It is of certain interest to use in this reaction supported catalysts having a more developed surface (compared to bulky catalysts) but containing a smaller amount of metal. The purpose of this work is to study the activity and selec tivity of a series of supported catalysts based on Ni, Pt, and Pd in the ...

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Liquid-phase hydroamination of cyclohexanone

et al. 2010

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“…is a potential alternative route, but it is thermodynamically limited and approaches to overcome this limitation by use of a cataloreactant [46] or coupled hydrogen consuming reactions [47] have proved unsuccessful.…”

Section: Potential Of Nitrides As Nitrogen Transfer Reagentsmentioning

confidence: 99%

Nitrides as ammonia synthesis catalysts and as potential nitrogen transfer reagents

Hargreaves

2014

Appl Petrochem Res

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“…At present, the industrial production of aniline is mainly in three ways, that is, catalytic hydrogenation of nitrobenzene, phenol amination and nitrobenzene iron reduction method, its production capacity is about 85.0%, 10.0% and 5.0% of the total production capacity of aniline, respectively. However, these methods characterized of higher cost, harsh operating conditions and environmental pollution, these do not accord with the concept of green chemistry and sustainable development . Through the activation of C‐H bond in benzene, amino groups will be directly introduced into the benzene ring to form aniline .…”

Section: Introductionmentioning

confidence: 99%

Research on the direct amination of benzene to aniline by NiAlPO₄–5 catalyst

Wang

Yang

Zhang

2019

Applied Organom Chemis

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A series of NiAlPO4–5 molecular sieves have been hydrothermally synthesized and shown high and stable activity in the direct amination of benzene to aniline with hydroxylamine hydrochloride as aminating agent. The as‐synthesized and calcined samples were investigated with XRD, SEM, TG, BET, NH3‐TPD and FT‐IR to explore the crystalline, coordination and location of the incorporated transition metal ions. The results indicated that nickel ions were incorporated into the framework of AlPO4–5 and the as‐synthesized catalysts were highly crystalline, and possessed good thermal stability. Among them, Ni(0.3)AlPO4–5 showed the highest catalytic activity for the direct amination of benzene with the highest aniline yield of 73.2% and 100.0% selectivity to aniline. After the catalyst was reused for 5 times, the activity remained little change.

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Amination of cyclohexanone and cyclohexanol/cyclohexanone in the presence of ammonia and hydrogen using copper or a group VIII metal supported on a carrier as the catalyst

Cited by 46 publications

References 12 publications

Liquid-phase hydroamination of cyclohexanone

Liquid-phase hydroamination of cyclohexanone

Nitrides as ammonia synthesis catalysts and as potential nitrogen transfer reagents

Research on the direct amination of benzene to aniline by NiAlPO₄–5 catalyst

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Amination of cyclohexanone and cyclohexanol/cyclohexanone in the presence of ammonia and hydrogen using copper or a group VIII metal supported on a carrier as the catalyst

Cited by 46 publications

References 12 publications

Liquid-phase hydroamination of cyclohexanone

Liquid-phase hydroamination of cyclohexanone

Nitrides as ammonia synthesis catalysts and as potential nitrogen transfer reagents

Research on the direct amination of benzene to aniline by NiAlPO4–5 catalyst

Contact Info

Product

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Research on the direct amination of benzene to aniline by NiAlPO₄–5 catalyst