Oxidation-extraction desulfurization of model oil over Zr-ZSM-5/SBA-15 and kinetic study

Abstract

ZSM-5/SBA-15 composite molecular sieves were synthesized using post-synthesis method and characterized by X-ray diffraction and N₂ adsorption-desorption. The oxidative-extration desulfurization of model oil was investigated by using hydrogen peroxide as the oxidant, tetrabutyl ammonium bromide as phase transfer catalyst, dimethyl sulfoxide as extractant, and Zr-ZSM-5/SBA-15, Ag-ZSM-5/SBA-15, Ce-ZSM-5/SBA-15 as catalyst. Under the optimal conditions, the desulfurization rate decreases in the order: Zr-ZSM-5/SBA-15>Ce-ZSM-5/SBA-15>Ag-ZSM-5/SBA-15. The highest desulfurization rate is 84.53% under the catalysis of Zr-ZSM-5/SBA-15. Kinetics analysis shows that the reaction is pseudo-first-order with the activation energy of 44.23 kJ/mol.

Key words： composite molecular sieve; oxidation desulfuration; extraction; kinetic

Acknowledgements

We acknowledge the Doctor financial support from Liaoning Province in China (Grant No. 20081104).

References

1 FuY, DiwekarU M. Cost effective environmental control technology for utilities. Advances in Environmental Research, 2004, 8(2): 173–196

2 SrivastavaR K, HallR E, KhanS, CulliganK, LaniB W. Nitrogen oxides emission control options for coal-fired electric utility boilers. Journal of the Air & Waste Management Association, 2005, 55(9): 1367–1388

3 GonzalezL A, KrackeP, GreenW H, TesterJ W, ShaferL M, TimkoM T. Oxidative desulfurization of middle-distillate fuels using activated carbon and power ultrasound. Energy & Fuels, 2012, 26(8): 5164–5176

4 LiX, BaiJ, WangA, PrinsR, WangY. Hydrodesulfurization of dibenzothiophene and its hydrogenated intermediates over bulk Ni₂P. Topics in Catalysis, 2011, 54(5–7): 290–298

5 FujikawaT. Highly active HDS catalyst for producing ultra-low sulfur diesel fuels. Topics in Catalysis, 2009, 52(6–7): 872–879

6 WangG, WenY, FanJ, XuC, GaoJ. Reactive characteristics and adsorption heat of Ni/ZnO-SiO₂-Al₂O₃ adsorbent by reactive adsorption desulfurization. Industrial & Engineering Chemistry Research, 2011, 50(22): 12449–12459

7 LiuY, SheN, ZhaoJ, PengT, LiuC. Fabrication of hierarchical porous ZnO and its performance in Ni/ZnO reactive-adsorption desulfurization. Petroleum Science, 2013, 10(4): 589–595

8 HuangC, ChenB, ZhangJ, LiuZ, LiY. Desulfurization of gasoline by extraction with new ionic liquids. Energy & Fuels, 2004, 18(6): 1862–1864

9 MaS C, YaoJ J, JinX, ZhangB. Kinetic study on desulfurization and denitrification using microwave irradiation over activated carbon. Science China Technological Sciences, 2011, 54(9): 2321–2326

10 BaezaP, AguilaG, GraciaF, ArayaP. Desulfurization by adsorption with copper supported on zirconia. Catalysis Communications, 2008, 9(5): 751–755

11 OtsukiS, NonakaT, TakashimaN, QianW, IshiharaA, ImaiT, KabeT. Oxidative desulfurization of light gas oil and vacuum gas oil by oxidation and solvent extraction. Energy & Fuels, 2000, 14(6): 1232–1239

12 ZannikosF, LoisE, StournasS. Desulfurization of petroleum fractions by oxidation and solvent extraction. Fuel Processing Technology, 1995, 42(1): 35–45

13 WangR, ZhangG, ZhaoH. Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil. Catalysis Today, 2010, 149(1–2): 117–121

14 TeM, FairbridgeC, RingZ. Oxidation reactivities of dibenzothiophenes in polyoxometalate/H₂O₂ and formic acid/H₂O₂ systems. Applied Catalysis A: General, 2001, 219(1–2): 267–280

15 ZhangY, LuH, WangL, ZhangY, LiuP, HanH, JiangZ, LiC. The oxidation of benzothiophene using the Keggin-type lacunary polytungstophosphate as catalysts in emulsion. Journal of Molecular Catalysis A: Chemical, 2010, 332(1–2): 59–64

16 ZhangY, WangL, ZhangY, JiangZ, LiC. Ultra-deep oxidative desulfurization of fuel oil catalyzed by Dawson-Type polyoxotungstate emulsion catalysts. Chinese Journal of Catalysis, 2011, 32(1): 235–239

17 LiX, HuangS, XuQ, YangY. Preparation of WO₃-SBA-15 mesoporous molecular sieve and its performance as an oxidative desulfurization catalyst. Transition Metal Chemistry, 2009, 34(8): 943–947

18 YingJ Y, SunT. Synthesis of microporous transition-metal-oxide molecular sieves by a supramoleculaur templating mechanism. Nature, 1997, 389(6652): 704–706

19 WangS, DouT, LiY, ZhangY, YanZ, LiX. Synthesis of a new meso/microporous composite molecular sieve of MCM-41 mordenite. Chinese Science Bulletin, 2005, 50(12): 1180–1184

20 PoladiR H P R, LandryC C. Synthesis, characterization and catalytic properties of a microporous/mesoporous material, MMM-1. Journal of Solid State Chemistry, 2002, 167(2): 363–369

21 Richard KloetstraK, JansenJ C. Mesoporous material containing framework tectosilicate by pore-wall recrystallization. Chemical Communications, 1997, (23): 2281–2282

22 TwaiqF A A, MohamadA R, BhatiaS. Performance of composite catalyst in palm oil cracking for the production of liquid fuels and chemicals. Fuel Processing Technology, 2004, 85(11): 1283–1300

23 LiangD, QinB, WangY, LiuJ H, LiR F. Direct preparation of Zr-SBA-15 microspheres and their catalytic performance on methanol dehydration. Journal of Fuel Chemistry and Technology, 2010, 38(5): 582–587

24 KrishnanC K, HayashiT, OguraM. A new method for post-synthesis coating of zirconia on the mesopore walls of SBA-15 without pore blocking. Advanced Materials, 2008, 20(11): 2131–2136

25 LiF, YuF, YiL, LiR, XieK. Direct synthesis of Zr-SBA-15 mesoporous molecular sieves with high zirconium loading: Characterization and catalytic performance after sulfated. Mieroporous Mesoporons Mater, 2007, 101(1–2): 250–255

26 LiangD, ChenJ, WangY J, LiuJ H, LiR F. Synthesis of Zr-containing SBA-15 with hollow spherical morphology. Chemistry Letters, 2009, 38(7): 672–673

27 JiS, LiaoS, WangL, VladmirL, LeslieP. Preparation and characterization of novel superacid catalyst SO42-/Zr-ZSM-5. Journal of Molecular Catalysis, 2002, 16(5): 379–383

28 XiaQ H, HidajatK, KawiS. Synthesis of SO42-/ZrO₂/MCM-41 as a new superacid catalyst. Chemical Communications, 2000, (22): 2229–2230

29 XiaQ H, HidajatK, KawiS. Effect of ZrO₂ loading on the structure,acidity and catalytic activity of the SO42-/ZrO₂/MCM-41 acid catalyst. Journal of Catalysis, 2002, 205(2): 318–331

30 ZhaoD, FengJ, HuoQ, MeloshN, FredricksonG H, ChmelkaB F, StuckyG D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science, 1998, 279(5350): 548–552

31 CaoL, DongH, HuangL, MatyjaszewskiK, KrukM. Synthesis of large-pore SBA-15 silica using poly(ethylene oxide)-poly(methyl acrylate) diblock copolymers. Adsorption, 2009, 15(2): 156–166

32 DongareM K, SinghP, MogheP P, RatnasamyP. Synthesis,characterization and catalytic properties of [Zr]-ZSM-5. Zeolites, 1991, 11(7): 690–693

33 YanB, ZhengZ, ZhangJ, GongZ, ShenZ, HuangW, YuT. Orientation controllable growth of MoO₃ nanoflakes: Micro-Raman, field emission and birefringence properties. Journal of Physical Chemistry C, 2009, 113(47): 20259–20263

34 JinC, MaB, ZhangX, LingF, ZhangZ, QinB. Study of hydrocracking of n-octane on Ni-Mo/Y-β catalyst. Industrial Catalysis, 2007, 15(12): 24–27 (in Chinese)

35 WangG, WangX, WangX, YuS. Synthesis and catalytic reaction of [Zr] ZSM-5. Studies in Surface Science and Catalysis, 1994, 83: 67–74

36 OthmanM R, MustafaN N N, AhmadA L. Effect of thermal treatment on the microstructure of sol-gel derived porous alumina modified platinum. Microporous and Mesoporous Materials, 2006, 91(1–3): 268–275

37 BozoC, GuilhaumeN, GarbowskiE, PrimetM. Combustion of methane on CeO₂-ZrO₂ based catalysts. Catalysis Today, 2000, 59(1–2): 33–45

38 ZhaoD, HuoQ, FengJ, ChmelkaB F, StuckyG D. Nonionic tribloek and star diblock copolymer and oligomeric surfactant syntheses of highly ordered,hydrothermally stable,mesoporous silica structures. Journal of the American Chemical Society, 1998, 120(24): 6024–6036

39 ZhengT, LuJ, ZhaoY. Review on cerium-based composite oxides as oxygen storage materials. Chinese Journal of Nonferrous Metals, 2013, 23(6): 1575–1581 (in Chinese)

40 KongL, LiG, WangX, WuB. Oxidative desulfurization of organic sulfur in gasoline overAg/TS-1. Energy & Fuels, 2006, 20(3): 896–902

41 YuX, RenX, DongZ, WangJ, WangY. Kinetics of the hydrodesulfurization of dibenzothiopyene over a commercial NiW/Al₂O₃ catalyst. Journal of Fuel Chemistry and Technology, 2005, 33(4): 483–486