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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2023, Vol. 17 Issue (1) : 82-92    https://doi.org/10.1007/s11705-022-2181-z
RESEARCH ARTICLE
Reductive amination of n-hexanol to n-hexylamine over Ni–Ce/γ-Al2O3 catalysts
Pengfei Li, Huijiang Huang, Zheng Wang, Ziying Hong, Yan Xu(), Yujun Zhao()
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
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Abstract

The amination of alkyl alcohols is one of the most promising paths in synthesis of aliphatic amines. Herein, cerium doped nickel-based catalysts were synthesized and tested in a gas-phase amination of n-hexanol to n-hexylamine. It was found that the activity of the Ni/γ-Al2O3 catalyst is significantly improved by doping an appropriate amount of cerium. The presence of cerium effectively inhibits the agglomeration of nickel particle, resulting in better Ni dispersion. As Ni particle size plays critical role on the catalytic activity, higher turnover frequency of n-hexanol amination was achieved. Cerium doping also improves the reduction ability of nickel and enhances the interactions between Ni and the catalyst support. More weak acid sites were also found in those cerium doped catalysts, which promote another key step—ammonia dissociative adsorption in this reaction system. The overall synergy of Ni nanoparticles and acid sites of this Ni–Ce/γ-Al2O3 catalyst boosts its superior catalytic performance in the amination of n-hexanol.

Keywords amination      alcohol      cerium      nickel      acidity      interaction     
Corresponding Author(s): Yan Xu,Yujun Zhao   
About author:

Changjian Wang and Zhiying Yang contributed equally to this work.
Online First Date: 01 August 2022    Issue Date: 21 February 2023
 Cite this article:   
Pengfei Li,Huijiang Huang,Zheng Wang, et al. Reductive amination of n-hexanol to n-hexylamine over Ni–Ce/γ-Al2O3 catalysts[J]. Front. Chem. Sci. Eng., 2023, 17(1): 82-92.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2181-z
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I1/82
Catalyst Metal loading a)/wt % SBETb)/(m2?g–1) Pore volume/(cm3?g–1) Pore diameter/(m3?g–1) Dispersionc)/% dNid)/nm dCee)/nm
Ni Ce
Ni–0Ce 9.77 0.00 133 0.23 4.7 18.0 3.9 –
Ni–1Ce 9.83 1.11 117 0.20 4.9 23.5 3.5 –
Ni–2Ce 9.97 1.96 122 0.20 4.8 24.9 2.7 3.1
Ni–3Ce 10.31 2.98 113 0.20 4.9 23.5 2.8 5.2
Ni–5Ce 9.87 5.26 117 0.19 4.8 21.8 3.2 5.5
Ni/CeO2 9.91 90.09 25 0.07 8.5 – 38.1 21.1
Tab.1  Texture properties and structure of Ni–Ce and Ni/CeO2
Fig.1  XRD results of the Ni–xCe and Ni/CeO2 catalysts: (a) calcined and (b) reduced.
Fig.2  TEM images of the catalysts: (a) Ni–0Ce; (b) Ni–0Ce; (c) Ni–2Ce; (d) Ni–2Ce.
Fig.3  (a) H2-TPR patterns of catalysts with different Ce contents, and (b) the areas composition of various peaks ascribed to the nickel species and their sums. α corresponding to the NiO that have weak interactions with the support, β corresponding to the NiO that have strong interactions with the support, γ represents NiAl2O4 (Ni–Al spinel).
Catalyst Temperature/°C–Peak area/a.u.
α β γ
Ni–0Ce 422.6–1.40 582.6–4.13 690.0–0.44
Ni–1Ce 414.3–0.83 579.7–3.38 685.6–0.39
Ni–2Ce 384.2–1.14 565.6–4.22 677.4–0.14
Ni–3Ce 391.1–1.15 568.7–3.29 675.9–0.34
Tab.2  The peak temperatures and peak areas characterized by the H2-TPR profiles of Ni–xCe catalysts
Catalyst H2 desorption temperature/°C–H2 desorption amount/(μmol?g–1)
Weak Moderate Strong Total
Ni–0Ce 121.9–92 258.9–239 503.1–118 449
Ni–1Ce 128.2–-83 231.2–208 484.5–389 681
Ni–2Ce 133.2–112 234.9–376 471.0–331 819
Ni–3Ce 130.1–87 226.4–302 486.8–493 882
Tab.3  Results for band deconvolution for H2-TPD profiles measured on the different catalytic formulation
Fig.4  (a) H2-TPD profiles of the Ni–xCe catalysts, and (b) the composition of the various hydrogen desorption peaks, and their sums.
Fig.5  NH3-TPD profiles of the Ni–xCe catalysts.
Catalyst Peak area of acidic sites/a.u.
Weak Strong Total
Ni–0Ce 125 136 262
Ni–1Ce 120 151 272
Ni–2Ce 117 294 365
Ni–3Ce 80 268 347
Tab.4  Results for band deconvolution for NH3-TPD profiles measured on the different catalytic formulation
Catalyst Binding energy/eV XNi0/% XNi2+ b)/%
Ni0 Ni2+ a) Ni2+ b)
Ni–0Ce 852.0 853.2 855.4 857.0 28.1% 16.2%
Ni–2Ce 852.0 853.4 855.4 857.0 30.5% 7.8%
Ni–3Ce 852.3 853.7 855.9 857.3 21.4% 15.0%
Tab.5  Deconvolution results of Ni 2p 3/2 on the surface of catalysts
Fig.6  XPS for (a) Ni 2p 3/2 and (b) Ce 3d.
Catalyst Binding energy/eV XCe3+
Ni–2Ce 885.8 904.0 45.6%
Ni–3Ce 885.3 903.6 49.2%
Tab.6  Deconvolution results of Ce 3d on the surface of catalysts
Fig.7  Catalytic amination performance of Ni–xCe at different GHSV: (a) Ni–0Ce, (b) Ni–1Ce, (c) Ni–2Ce, (d) Ni–3Ce, and (e) Ni–5Ce. Reaction conditions: 0.25 g cat., T = 200 °C, P = 0.1 MPa, hexanol:H2:NH3 = 1:9:11.
Fig.8  Stability of Ni–0Ce and Ni–2Ce: (a) Ni–0Ce and (b) Ni–2Ce. Reaction conditions: 0.25 g cat.,T = 200 °C, P = 0.1 MPa, GHSV = 7.91 min–1, hexanol:H2:NH3= 1:9:11.
Fig.9  The effect of (a) nickel particle size and (b) the number of acid amount on TOF of n-hexanol amination. Reaction conditions: 0.25 g cat., T = 200 °C, P = 0.1 MPa, GHSV = 19.78 min–1, hexanol:H2:NH3= 1:9:11.
  Scheme1 Proposed reaction mechanism for hexanol amination over Ni–xCe catalyst.
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