Citation: LIU Di, TONG Huan, YUAN Linjie, ZHANG Zipeng, MA Kangfu, YUAN Lin, ZHANG Wanyu, CHEN Lidong, WANG Xiangsheng, GUO Hongchen. Preparation of High Activity Oxidative Desulfurization Catalyst from Phosphomolybdic Acid and Titania Silica Nanocomposite[J]. Chinese Journal of Applied Chemistry, ;2018, 35(11): 1351-1356. doi: 10.11944/j.issn.1000-0518.2018.11.170462 shu

Preparation of High Activity Oxidative Desulfurization Catalyst from Phosphomolybdic Acid and Titania Silica Nanocomposite

LIU Di ^a ,
TONG Huan ^a ,
YUAN Linjie ^a ,
ZHANG Zipeng ^a ,
MA Kangfu ^a ,
YUAN Lin ^a ,
ZHANG Wanyu ^a ,
CHEN Lidong ^a,, ,
WANG Xiangsheng ^b ,
GUO Hongchen ^b,,

a.
Faculty of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, Liaoning 110629, China
b.
School of Chemistry Engineering, Dalian University of Technology, Dalian, Liaoning 116024, China

Corresponding author: CHEN Lidong, lidongchhm0809@163.com GUO Hongchen, hongchenguo@dlut.edu.cn
Received Date: 21 December 2017
Revised Date: 31 January 2018
Accepted Date: 8 March 2018

Fund Project: the Innovation and Entrepreneurship Project of College Students in Liaoning 201710165000363Supported by the Innovation and Entrepreneurship Project of College Students in Liaoning(No.201710165000363)

Figures(6)

High-performance titania-silica (TiO₂-SiO₂) nanocomposites were synthesized with a sol gel method. The composite catalyst was prepared by either in situ synthesis (HPMo-TiO₂-SiO₂-is) or the impregnation method (HPMo/TiO₂-SiO₂) using Keggin-structure phosphomolybdic acid and TiO₂-SiO₂. The structures of these catalysts were characterized by scanning electron micrographs (SEM), Fourier transform infrared spectrum (FT-IR), ultraviolet visible spectroscopy (UV-Vis), Brunauer-Emmett-Teller (BET) and X-ray powder diffraction pattern (XRD). The preservation of the Keggin structure in HPMo-TiO₂-SiO₂-is and HPMo/TiO₂-SiO₂ catalysts was confirmed. The results show that the synthesized catalysts are in nanometer size and the micropores and mesopores coexist. The catalytic oxidation desulfurization reaction was studied over synthesized catalysts with a model oil (n-octane solution of organic sulfur). Reaction conditions are listed as following:model oil/ethanol=10.0 mL/10.0 mL, catalyst 0.15 g, n (O)/n (S)=5, temperature 30~70℃ and time=3 h. It is clear that the catalytic properties of the HPMo-TiO₂-SiO₂-is and HPMo/TiO₂-SiO₂ are similar under optimized conditions. The conversion of dibenzothiophene is 96.0% and the content of sulphur is below 10 μg/g. Under the same conditions, the efficiencies of oxidative desulfurization decrease in the order of dibenzothiophene > benzothiophene > thiophene, and the result is influenced by the electron density on the sulfur atoms. The catalytic activity of the recycled HPMo-TiO₂-SiO₂-is catalyst is almost as the same as that of freshly prepared. The HPMo-TiO₂-SiO₂-is and HPMo/TiO₂-SiO₂ catalysts could be recycled and easily separated. These catalysts used herein are an ideal model for oxidation desulfurization of sulfur compounds.
- phosphomolybdic acid,
- titania-silica nanocomposite,
- oxidative desulfurization,
- Sol Gel method,
- hydrogen peroxide
1. [1]
  Song C S. An Overview of New Approaches to Deep Desulfurization for Ultra-Clean Gasoline, Diesel Fuel and Jet Fuel[J]. Catal Today, 2003,86(1/2/3/4):211-263.
2. [2]
  Ji H Y, Sun J, Wu P W. Silicotungstic Acid Immobilized on Lamellar Hexagonal Boron Nitride for Oxidative Desulfurization of Fuel Components[J]. Fuel, 2018,213(1):12-21.
3. [3]
  Dizaji A K, Mortaheb H R, Mokhtarani B. Complete Oxidative Desulfurization Using Graphene Oxide-Based Phosphomolybdic Acid Catalyst:Process Optimization by Two Phase Mass Balance Approach[J]. Chem Eng J, 2018,335(1):362-372.
4. [4]
  Shen C, Wang Y J, Xu J H. Synthesis of TS-1 on Porous Glass Beads for Catalytic Oxidative Desulfurization[J]. Chem Eng J, 2015,259(1):552-561.
5. [5]
  Kong L Y, Li G, Wang X S. Mild Oxidation of Thiophene over TS-1/H₂O₂[J]. Catal Today, 2004,93/94/95(1):341-345.
6. [6]
  Du S T, Li F, Sun Q M. A Green Surfactant-Assisted Synthesis of Hierarchical TS-1 Zeolites with Excellent Catalytic Properties for Oxidative Desulfurization[J]. Chem Commun, 2016,52(16):3368-3370. doi: 10.1039/C5CC08441E
7. [7]
  Du S T, Chen X X, Sun Q M. A Non-chemically Selective Top-Down Approach Towards the Preparation of Hierarchical TS-1 Zeolites with Improved Oxidative Desulfurization Catalytic Performance[J]. Chem Commun, 2016,52(17):3580-3583. doi: 10.1039/C5CC10232D
8. [8]
  Du S T, Sun Q M, Wang N. Synthesis of Hierarchical TS-1 Zeolites with Abundant and Uniform Intracrystalline Mesopores and Their Highly Efficient Catalytic Performance for Oxidation Desulfurization[J]. J Mater Chem A, 2017,5(17):7992-7998. doi: 10.1039/C6TA10044A
9. [9]
  Jin C Z, Li G, Wang X S. Synthesis, Characterization and Catalytic Performance of Ti-Containing Mesoporous Molecular Sieves Assembled from Titanosilicate Precursors[J]. Chem Mater, 2007,19(7):1664-1670. doi: 10.1021/cm0625777
10. [10]
  Bazyari A, Khodadadi A A, Mamaghani A H. Microporous Titania Silica Nanocomposite Catalyst Adsorbent for Ultra-deep Oxidative Desulfurization[J]. Appl Catal B:Environ, 2016,180(1):65-77.
11. [11]
  Lv H Y, Ren W Z, Liao W P. Aerobic Oxidative Desulfurization of Model Diesel Using a B-type Anderson Catalyst[(C₁₈H₃₇)₂N(CH₃)₂]₃Co(OH)₆Mo₆O₁₈·3H₂O[J]. Appl Catal B:Environ, 2013,138/139(1):79-83.
12. [12]
  Li C, Jiang Z X, Gao J B. Ultra-deep Desulfurization of Diesel:Oxidation with a Recoverable Catalyst Assembled in Emulsion[J]. Chem-Eur J, 2004,10(9):2277-2280. doi: 10.1002/(ISSN)1521-3765
13. [13]
  CHEN Lidong, LIU Di, NIU Siqi. Oxidative Desulfurization of Organic Sulfides over Phosphotungstic Acid/Nano-ZSM-5 Composite Catalyst[J]. Chinese J Appl Chem, 2016,33(3):364-366.
14. [14]
  CHEN Lidong, TONG Huan, WANG Xuyang. Preparation of High Activity Oxidative Desulfurization Catalyst with Polycation and Heteropolyanion Keggin Structure[J]. Chinese J Appl Chem, 2017,34(11):1301-1306. doi: 10.11944/j.issn.1000-0518.2017.11.170011
15. [15]
  Chen L D, Wang X S, Guo X W. In Situ Nanocrystalline HZSM-5 Zeolites Encaged Heteropoly Acid H₃PMo₁₂O₄₀ and Ni Catalyst for Hydroconversion of n-Octane[J]. Chem Eng Sci, 2007,62(16):4469-4478. doi: 10.1016/j.ces.2007.05.013
16. [16]
  Guo Q, Sun K J, Feng Z C. A Thorough Investigation of the Active Titanium Species in TS-1 Zeolite by in Situ UV Resonance Raman Spectroscopy[J]. Chem-A Eur J, 2012,18(43):13854-13860. doi: 10.1002/chem.201201319
17. [17]
  Zhu W S, Huang W L, Li H M. Polyoxometalate-Based Ionic Liquids as Catalysts for Deep Desulfurization of Fuels[J]. Fuel Process Tech, 2011,92(10):1842-1848. doi: 10.1016/j.fuproc.2011.04.030
18. [18]
  Otsuki S, Nonaka T, Takashima N. Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extraction[J]. Energy Fuels, 2000,14(6):1232-1239. doi: 10.1021/ef000096i
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