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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.    2022, Vol. 16 Issue (8) : 1224-1236    https://doi.org/10.1007/s11705-022-2139-1
RESEARCH ARTICLE
The modification of titanium in mesoporous silica for Co-based Fischer–Tropsch catalysts
Xin Li1,2,3, Meng Su1,2, Yao Chen1,2, Mehar U. Nisa1,2, Ning Zhao1,2, Xiangning Jiang1,2, Zhenhua Li1,2()
1. Key Lab for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
2. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China
3. Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China
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Abstract

Ordered SBA-15 mesoporous silica with incorporated titanium was successfully synthesized via a one-pot hydrothermal crystallization method. The characterization including powder X-ray diffraction, Brunauer–Emmett–Teller, transmission electron microscope, temperature-programmed reduction, temperature-programmed desorption, Fourier transform infrared and ultraviolet-visible-near infrared spectrometer was performed to explore the physical and chemical structures of both the supports and the catalysts. The results showed that titanium was successfully incorporated into the mesoporous silica framework with a limited amount of titanium (Si/Ti > 20), and the mesoporous structure was retained. However, the increased titanium content inevitably resulted in the formation of anatase TiO 2 particles on the support surface. The increased incorporated titanium strengthened the interactions between cobalt species and supports, which was favorable for the cobalt species dispersion, despite the limited cobalt oxide reducibility. The enhanced metal-support interactions were beneficial for the CO/H2 ratio at the active cobalt sites, which facilitated the formation of more C5+ hydrocarbons. This study provides a promising method for support modification with incorporated-heteroatoms for the rational development of Fischer–Tropsch catalysts.

Keywords Fischer–Tropsch synthesis      titanium incorporation      mesoporous silica      metal-support interactions      C5+ selectivity     
Corresponding Author(s): Zhenhua Li   
Online First Date: 19 April 2022    Issue Date: 02 August 2022
 Cite this article:   
Xin Li,Meng Su,Yao Chen, et al. The modification of titanium in mesoporous silica for Co-based Fischer–Tropsch catalysts[J]. Front. Chem. Sci. Eng., 2022, 16(8): 1224-1236.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2139-1
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I8/1224
Fig.1  SXRD patterns of (a) supports and (b) fresh catalysts.
Sample Si/Ti ratio SBET/(m2·g−1) a) Vt/(cm3·g−1) b) DP/nm c)
SBA-15 +∞ 815 1.12 6.72
OMST80 80 556 0.73 6.54
OMST60 60 491 0.72 6.31
OMST40 40 452 0.67 6.30
OMST20 20 494 0.78 6.20
OMST10 10 470 0.87 6.25
Co/SBA-15 +∞ 472 0.61 6.28
Co/OMST80 80 462 0.55 6.29
Co/OMST60 60 464 0.64 6.30
Co/OMST40 40 411 0.60 5.98
Co/OMST20 20 425 0.60 5.73
Tab.1  Textural properties of the prepared samples
Fig.2  Textural properties of supports and catalysts: N2 adsorption-desorption isotherms of (a) supports and (b) catalysts; mesopore size distribution of (c) supports and (d) catalysts.
Sample SBA-15 OMST80 OMST60 OMST40 OMST20 OMST10
Si/Ti +∞ 80 60 40 20 10
Theoretical Ti/wt% 0 0.98 1.30 1.93 3.73 7.03
Actual Ti/wt% 0 0.95 1.26 1.86 3.60 6.86
Loss ratio/wt% 0 3.01 3.00 3.50 3.61 2.44
Tab.2  Theoretical and experimentally obtained Ti content in OMSTx
Fig.3  FTIR spectra of SBA-15 and OMSTx supports.
Fig.4  UV-visible absorption spectra of SBA-15 and OMSTx supports.
Fig.5  TEM images of SBA-15 and OMSTx supports.
Fig.6  EDX-mapping images of OMST80 and OMST10 supports.
Fig.7  Wide-angle XRD patterns of (a) SBA-15 and OMSTx and (b) Co/SBA-15 and Co/OMSTx.
Catalyst Co/SBA-15 Co/OMST80 Co/OMST60 Co/OMST40 Co/OMST20 Co/OMST10
Co3O4 size from XRD a)/nm 15.3 11.7 11.7 11.7 11.3 11.2
Co3O4 size from TEM b)/nm 11.94 10.81 10.46 10.57 10.38 9.98
Tab.3  Co3O4 particle size obtained from XRD results and TEM images
Fig.8  TEM images of fresh Co/SBA-15 and Co/OMSTx catalysts.
Fig.9  H2-TPR profiles of Co/SBA-15 and Co/OMSTx catalysts.
Fig.10  (a) H2-TPD and (b) CO-TPD profiles for Co/SBA-15 and Co/OMSTx catalysts.
Catalyst Adsorbed CO/(mmol·gCo−1) Adsorbed H2/(mmol·gCo−1) CO/H2 ratio
Co/SBA-15 0.28 0.14 2.00
Co/OMST80 0.25 0.11 2.27
Co/OMST60 0.20 0.09 2.22
Co/OMST40 0.19 0.09 2.11
Co/OMST20 0.01 0.01 1.00
Co/OMST10 0.01 0.01 1.00
Tab.4  Quantitative CO-TPD and H2-TPD data of Co/SBA-15 and Co/OMSTx a)
Catalyst a) XCO/% CTYc)/(10−4 molCO·gCo−1·s−1) CO2 selectivity/% Hydrocarbon selectivity/% C=/C–(C2−4)
CH4 C2 C3 C4 C5+
Co/SBA-15 b) 69.0 1.02 1.2 20.6 2.2 4.6 3.9 68.8 0.23
Co/OMST80 47.28 0.70 1.3 13.91 1.21 3.43 3.59 77.66 0.50
Co/OMST60 42.91 0.63 1.2 14.94 1.42 4.02 4.23 75.39 0.52
Co/OMST40 40.05 0.59 1.1 15.25 1.47 4.05 4.15 75.09 0.52
Co/OMST20 25.32 0.38 1.0 17.40 2.33 6.55 6.31 67.42 0.99
Co/OMST10 23.29 0.34 1.0 18.47 2.35 6.71 6.95 65.52 0.80
Tab.5  FTS results of Co/SBA-15 and CO/OMSTx
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