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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

邮发代号 80-969

2019 Impact Factor: 3.552

Frontiers of Chemical Science and Engineering  2023, Vol. 17 Issue (2): 139-155   https://doi.org/10.1007/s11705-022-2217-4
  本期目录
Efficient hydrothermal deoxygenation of methyl palmitate to diesel-like hydrocarbons on carbon encapsulated Ni–Sn intermetallic compounds with methanol as hydrogen donor
Haonan Shi, Xiaoyu Gu, Yinteng Shi, Dandan Wang, Sihao Shu, Zhongze Wang, Jixiang Chen()
Tianjin Key Laboratory of Applied Catalysis Science and Technology, Department of Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
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Abstract

Porous carbon-encapsulated Ni and Ni–Sn intermetallic compound catalysts were prepared by the one-pot extended Stöber method followed by carbonization and tested for in-situ hydrothermal deoxygenation of methyl palmitate with methanol as the hydrogen donor. During the catalyst preparation, Sn doping reduces the size of carbon spheres, and the formation of Ni–Sn intermetallic compounds restrain the graphitization, contributing to larger pore volume and pore diameter. Consequently, a more facile mass transfer occurs in carbon-encapsulated Ni–Sn intermetallic compound catalysts than in carbon-encapsulated Ni catalysts. During the in-situ hydrothermal deoxygenation, the synergism between Ni and Sn favors palmitic acid hydrogenation to a highly reactive hexadecanal that easily either decarbonylate to n-pentadecane or is hydrogenated to hexadecanol. At high reaction temperature, hexadecanol undergoes dehydrogenation–decarbonylation, generating n-pentadecane. Also, the C–C bond hydrolysis and methanation are suppressed on Ni–Sn intermetallic compounds, favorable for increasing the carbon yield and reducing the H2 consumption. The n-pentadecane and n-hexadecane yields reached 88.1% and 92.8% on carbon-encapsulated Ni3Sn2 intermetallic compound at 330 °C. After washing and H2 reduction, the carbon-encapsulated Ni3Sn2 intermetallic compound remains stable during three recycling cycles. This is ascribed to the carbon confinement that effectively suppresses the sintering and loss of metal particles under harsh hydrothermal conditions.

Key wordsextended Stöber method    carbon encapsulated Ni–Sn intermetallic compounds    confinement    in-situ hydrothermal deoxygenation    hydrogenation    decarbonylation
收稿日期: 2022-04-27      出版日期: 2023-02-27
Corresponding Author(s): Jixiang Chen   
作者简介:

Qingyong Zheng and Ya Gao contributed equally to this work.

 引用本文:   
. [J]. Frontiers of Chemical Science and Engineering, 2023, 17(2): 139-155.
Haonan Shi, Xiaoyu Gu, Yinteng Shi, Dandan Wang, Sihao Shu, Zhongze Wang, Jixiang Chen. Efficient hydrothermal deoxygenation of methyl palmitate to diesel-like hydrocarbons on carbon encapsulated Ni–Sn intermetallic compounds with methanol as hydrogen donor. Front. Chem. Sci. Eng., 2023, 17(2): 139-155.
 链接本文:  
https://academic.hep.com.cn/fcse/CN/10.1007/s11705-022-2217-4
https://academic.hep.com.cn/fcse/CN/Y2023/V17/I2/139
  
Fig.1  
Fig.2  
Fig.3  
Fig.4  
Fig.5  
CatalystSBET/(m2·g–1)Smic/(m2·g–1)Sext/(m2·g–1)Vmic/(cm3·g–1)Vmes/(cm3·g–1)dmic/nmdmes/nm
Ni@C14562830.0670.1190.485.3
Ni–Sn(3/1)@C293233590.1450.1250.418.5
Ni–Sn(3/1.8)@C354288660.1770.1480.408.4
Ni–Sn(1/1)@@C349286630.1740.1770.4010.7
Ni–Sn(3/1.8)@C-useda)6317460.0280.1350.6210.6
Tab.1  
Fig.6  
Fig.7  
  
Fig.8  
Fig.9  
EntrySolventReaction atmosphereReactantYield/%Gas phase composition/(mmol %)
18 mL water1 MPa N23.80 g palmitic acidn-C15: 5.0H2: 66.7CO2: 33.3
28 mL water3 MPa H2, 1 MPa N23.80 g palmitic acidn-C15: 61.7n-C16: 5.0hexadecanol: 14.9H2: 89.8CO2: 10.2
38 mL cyclohexane3 MPa H2, 1 MPa N23.80 g palmitic acid n-C15: 50.0n-C16: 15.2hexadecanol: 16.3H2: 90.2CO: 4.4CO2: 4.6CH4: 0.6
48 mL cyclohexane1 MPa N23.59 g hexadecanol n-C15: 79.1n-C16: 7.2H2: 50CO: 40.5CO2: 2.7CH4: 6.9
58 mL water1 MPa N23.59 g hexadecanoln-C15: 53.3n-C16: 4.3palmitic acid: 25.4H2: 76.8CO2: 22.4CH4:0.8
68 mL water3 MPa H2, 1 MPa N23.59 g hexadecanoln-C15: 84.6n-C16: 3.4H2: 88.4CO2: 10.9CH4: 0.7
Tab.2  
Fig.10  
  
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