Citation: YIN Hai-liang, LIU Xin-liang, ZHOU Tong-na, ZHAO Jian, LIN Ai-guo. Effect of ethylene glycol on the hydrogenation performance of P-doped NiMo/Al₂O₃ catalysts[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(12): 1458-1467. shu

Effect of ethylene glycol on the hydrogenation performance of P-doped NiMo/Al₂O₃ catalysts

1.
Academy of Science & Technology, China University of Petroleum(East China), Dongying 257061, China
2.
Environmental Protection Agency of Dongying, Dongying 257091, China

Corresponding author: YIN Hai-liang, yinhl@upc.edu.cn
Received Date: 22 July 2019
Revised Date: 17 October 2019

Fund Project: Fundamental Research Funds for the Central Universities 19CX02063Athe National Natural Science Foundation of China 21206197The project was supported by the National Natural Science Foundation of China (21206197), Shandong Provincial Natural Science Foundation (ZR2019MB022), Fundamental Research Funds for the Central Universities (19CX02063A)Shandong Provincial Natural Science Foundation ZR2019MB022

Figures(8)

NiMoP(x)/Al₂O₃ catalysts with different ethylene glycol (EG) contents were prepared by impregnating NiMoP solution containing EG into Al₂O₃. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) performances of the catalysts were evaluated using dibenzothiophene (DBT) and quinoline (Q) as the model compounds. The results showed that the HDS and HDN performances of the catalysts could be improved by adding of EG when the amount of EG was low (n_EG/n_Ni ratio value was 0, 0.5, 1, 2, 3, respectively), and the improvement of HDN performance was more obvious than HDS performance. With the increase of EG content, the activity of HDS and HDN of the catalysts was further improved. TEM and XPS analysis showed that EG was helpful to increase the stacking layer number and lamellar length of MoS₂ particles in the catalysts, and with the increase of EG content, the stacking layer number and lamellar length of MoS₂ particles increased. EG could improve the surface atomic concentration of Mo, but practically had no influence on the surface atomic distribution of Ni. However, EG significantly increased the sulfuration degree of Mo and Ni. TG characterization showed that EG interacted with alumina and metal active components in various ways, and there were high temperature resistant organic species interacting with active components.
- ethylene glycol,
- catalyst,
- hydrodesulfurization,
- hydrodenitrogenation
1. [1]
  GAO Y, HAN W, LONG X Y. Preparation of hydrodesulfurization catalysts using MoS₃ nanoparticles as a precursor[J]. Appl Catal B:Environ, 2018,224:330-340. doi: 10.1016/j.apcatb.2017.10.046
2. [2]
  PRAJAPATI Y N, VERMA N. Hydrodesulfurization of thiophene on activated carbon fiber supported NiMo catalysts[J]. Energy Fuels, 2018,32(2):2183-2196.
3. [3]
  XU Yan-chun, LI Xiang, WANG An-jie, YU Zhi-quan, CHEN Yong-ying. Influence of lanthanum oxide on the hydrodenitrogenation performance of bulk MoP[J]. Acta Pet Sin (Pet Process Sect), 2018,34(1):115-122. doi: 10.3969/j.issn.1001-8719.2018.01.016
4. [4]
  NICOSIA D, PRINS R. The effect of glycol on phosphate-doped CoMo/Al₂O₃ hydrotreating catalysts[J]. J Catal, 2005,229(2):424-438. doi: 10.1016/j.jcat.2004.11.014
5. [5]
  VAN HAANDEL L, BREMMER G M, HENSEN E J M, WEBER T. The effect of organic additives and phosphoric acid on sulfiation and activity of (Co)Mo/Al₂O₃ hydrodesulfurization catalysts[J]. J Catal, 2017,351:95-106. doi: 10.1016/j.jcat.2017.04.012
6. [6]
  NICOSIA D, PRINS R. The effect of phosphate and glycol on the sulfidation mechanism of CoMo/Al₂O₃ hydrotreating catalysts:An in situ QEXAFS study[J]. J Catal, 2005,231(2):259-268. doi: 10.1016/j.jcat.2005.01.018
7. [7]
  STANISLAUS A, MARAFI A, RANA M S. Recent advances in the science and technology of ultra-low sulfur diesel (ULSD) production[J]. Catal Today, 2010,153(1/2):1-68.
8. [8]
  ITO E, VAN VEEN J A R. On novel processes for removing sulphur from refinery streams[J]. Catal Today, 2006,116(4):446-460. doi: 10.1016/j.cattod.2006.06.040
9. [9]
  PIMERZIN A, MOZHAEV A, VARAKIN A, MASLAKOV K, NIKULSHIN P. Comparison of citric acid and glycol effects on the state of active phase species and catalytic properties of CoPMo/Al₂O₃ hydrotreating catalysts[J]. Appl Catal B:Environ, 2017,205:93-103. doi: 10.1016/j.apcatb.2016.12.022
10. [10]
  ESCOBAR J, BARRERA M C, TOLEDO J A, CORTES-JACOME M A, ANGELES-CHAVEZ C, NUNEZ S, SANTES V, GOMEZ E, DIAZ L, ROMERO E, PACHECO J G. Effect of ethyleneglycol addition on the properties of P-doped NiMo/Al₂O₃ HDS catalysts:Part Ⅰ. Materials preparation and characterization[J]. Appl Catal B:Environ, 2009,88(3/4):564-575.
11. [11]
  IWAMOTO R, KAGAMI N, SAKODA Y, IINO A. Effect of polyethylene glycol addition on NiO-MoO₃/Al₂O₃ and NiO-MoO₃-P₂O₅/Al₂O₃ hydrodesulfurization catalyst[J]. J Jpn Pet Inst, 2005,48(6):351-357. doi: 10.1627/jpi.48.351
12. [12]
  HAN Wen-peng, ZHANG Ye, LI Xue-kuan, TANG Xing-ming, ZHOU Li-gong, WU Ming-hong, GE Hui. Effect of coordinating groups of chelating agents on the hydrodesulfurization over CoMo/Al₂O₃ catalysts[J]. J Fuel Chem Technol, 2017,45(11):1332-1339. doi: 10.3969/j.issn.0253-2409.2017.11.008
13. [13]
  ROB VAN VEEN J A. What's new? On the development of sulphidic HT catalysts before the molecular aspects[J]. Catal Today, 2017,292:2-25. doi: 10.1016/j.cattod.2016.09.027
14. [14]
  COSTA V, GUICHARD B, DIGNE M, LEGENS C, LECOUR P, MARCHAND K, RAYBAUD P, KREBS E, GEANTET C. A rational interpretation of improved catalytic performances of additive-impregnated dried CoMo hydrotreating catalysts:A combined theoretical and experimental study[J]. Catal Sci Technol, 2013,3(1):140-151. doi: 10.1039/C2CY20553J
15. [15]
  NGUYEN T S, LORIDANT S, CHANTAL L, CHOLLEY T, GEANTET C. Effect of glycol on the formation of active species and sulfidation mechanism of CoMoP/Al₂O₃ hydrotreating catalysts[J]. Appl Catal B:Environ, 2011,107(1/2):59-67.
16. [16]
  IWAMOTO R, KAGAMI N, IINO A. Effect of polyethylene glycol addition on hydrodesulfurization activity over CoO-MoO₃/Al₂O₃ catalyst[J]. J Jpn Pet Inst, 2005,48(4):237-242. doi: 10.1627/jpi.48.237
17. [17]
  GUTIERREZ-ALEJANDRE A, LAURRABAQUIO-ROSAS G, RAMIREZ J, BUSCA G. On the role of triethyleneglycol in the preparation of highly active Ni-Mo/Al₂O₃ hydrodesulfurization catalysts:A spectroscopic study[J]. Appl Catal B:Environ, 2015,166/167:560-567. doi: 10.1016/j.apcatb.2014.11.039
18. [18]
  ALEXEY L N, GALINA A B, ALEKSANDER A P, IGOR P P, IRINA V D, VLADIMIR A V, EVGENY Y G, EVGENIYA N V, VALERII I B. Effect of Mono-, Di-, and triethylene glycol on the activity of phosphate-doped NiMo/Al₂O₃ hydrotreating catalysts[J]. Catalysts, 2019,9(1)96.
19. [19]
  LUO Xi-hui, HE Jin-hai. A Catalyst Impregnate and Its Preparation Method: CN, 961090480[P]. 2000-11-01.
20. [20]
  FERDOUS D, DALAI A K, ADJAYE J. A series of NiMo/Al₂O₃ catalysts containing boron and phosphorous Part Ⅰ. Synthesis and characterization[J]. Appl Catal A:Gen, 2004,260(1):137-151.
21. [21]
  QU L L, ZHANG W P, KOOYMAN P J, PRINS R. MAS NMR, TPR, and TEM studies of the interaction of NiMo with alumina and silica-alumina supports[J]. J Catal, 2003,215(1):7-13.
22. [22]
  SOLIS D, AGUDO A L, RAMIREZ J, KLIMOVA T. Hydrodesulfurization of hindered dibenzothiophenes on bifunctional NiMo catalysts supported on zeolite-alumina composites[J]. Catal Today, 2006,116(4):469-477.
23. [23]
  SUN M Y, KOOYMAN P J, PRINS R. A high-resolution transmission electron microscopy study of the influence of fluorine on the morphology and dispersion of WS₂ in sulfided W/Al₂O₃ and NiW/Al₂O₃ catalysts[J]. J Catal, 2002,206(2):368-375.
24. [24]
  HENSEN E J M, KOOYMAN P J, VAN DER MEER Y, VAN DER KRAAN A M, DE BEER V H J, VAN VEEN J A R, VAN SANTEN R A. The relation between morphology and hydrotreating activity for supported MoS₂ particles[J]. J Catal, 2001,199(2):224-235.
25. [25]
  VRADMAN L, LANDAU M V, HERSKOWITZ M. Hydrodearomatization of petroleum fuel fractions on silica supported Ni-W sulphide with increased stacking number of the WS₂ phase[J]. Fuel, 2003,82(6):633-639. doi: 10.1016/S0016-2361(02)00354-X
26. [26]
  FARAG H, SAKANISHI K, KOUZU M, MATSUMURA A, SUGIMOTO Y, SALTO I. Dibenzothiophene hydrodesulfurization over synthesized MoS₂ catalysts[J]. J Mol Catal A:Chem, 2003,206(1/2):399-408.
27. [27]
  SHIDO T, PRINS R. Why EXAFS underestimated the size of small supported MoS₂ particles[J]. J Phys Chem B, 1998,102(43):8426-8435. doi: 10.1021/jp982322j
28. [28]
  CALAIS C, MATSUBAYASHI N, GEANTET C, YOSHIMURA Y, SHIMADA H, NISHIJIMA A, LACROIX M, BREYSSE M. Crystallite size determination of highly dispersed unsupported MoS₂ catalysts[J]. J Catal, 1998,174(2):130-141. doi: 10.1006/jcat.1998.1934
29. [29]
  DE LA ROSA M P, TEXIER S, BERHAULT G, CAMACHO A, YACAMAN M J, MEHTA A, FUENTES S, MONTOYA J A, MURRIETA F, CHIANELLI R R. Structural studies of catalytically stabilized model and industrial-supported hydrodesulfurization catalysts[J]. J Catal, 2004,225(2):288-299.
30. [30]
  CHIANELLI R R. Periodic trends transition metal sulfide catalysis:Intuition and theory[J]. Oil Gas Sci Technol, 2006,61(4):503-513. doi: 10.2516/ogst:2006022a
31. [31]
  EIJSBOUTS S. On the flexibility of the active phase in hydrotreating catalysts[J]. Appl Catal A:Gen, 1997,158(1/2):53-92.
32. [32]
  KASZTELAN S, TOULHOAT H, GRIMBLOT J, BONNELLE J P. A geometrical model of the active phase of hydrotreating catalysts[J]. Appl Catal, 1984,13(1):127-159.
33. [33]
  BRAUN S, APPEL L G, SCHMAL M. Molybdenum species on alumina and silica supports for soot combustion[J]. Catal Commun, 2005,6(1):7-12.
34. [34]
  SHAHEEN W M. Thermal behaviour of pure and binary basic nickel carbonate and ammonium molybdate systems[J]. Mater Lett, 2002,52(4/5):272-282.
35. [35]
  GRIBOVAL A, BLACHARD P, PAYEN E, FOURNIER M, DUBOIS J L. Alumina supported HDS catalysts prepared by impregnation with new heteropolycompounds. Comparison with catalysts prepared by conventional Co-Mo-P coimpregnation[J]. Catal Today, 1998,45(1/4):277-283.
36. [36]
  GRIBOVAL A, BLANCHARD P, GENGEMBRE L, PAYEN E, FOURNIER M, DUBOIS J L, BERNARD J R. Hydrotreatment catalysts prepared with heteropolycompound:Characterization of the oxidic precursors[J]. J Catal, 1999,188(1):102-110.
37. [37]
  SARAVANAN L, SUBRAMANIAN S. Surface chemical studies on the competitive adsorption of poly(ethylene glycol) and ammonium poly(methacrylate) onto alumina[J]. J Colloid Interf Sci, 2005,284(2):363-377. doi: 10.1016/j.jcis.2004.08.188
38. [38]
  PORTELA L, GRANGE P, DELMON B. XPS and NO adsorption studies on alumina-supported Co-Mo catalysts sulfided by different procedures[J]. J Catal, 1995,156(2):243-254.
39. [39]
  DAMYANOVA S, PETROV L, GRANGE P. XPS characterization of zirconium-promoted CoMo hydrodesulfurization catalysts[J]. Appl Catal A:Gen, 2003,239(1/2):241-252.
40. [40]
  ATANASOVA P, HALACHEV T, UCHYTIL J, KRAUS M. Effect of phosphorus on the surface concentration of molybdenum and nickel in the oxide form of nickel-molybdenum-alumina catalysts and on their hydrodesulfurization activity[J]. Appl Catal, 1988,38:235-240. doi: 10.1016/S0166-9834(00)82828-6
41. [41]
  WANG X Q, OZKAN U S. Characterization of active sites over reduced Ni-Mo/Al₂O₃ catalysts for hydrogenation of linear aldehydes[J]. J Phys Chem B, 2005,109(5):1882-1890. doi: 10.1021/jp046489q
42. [42]
  VENEZIA A M, LA PAROLA V, DEGANELLO G, CAUZZI D, LEONARDI G, PREDIERI G. Influence of the preparation method on the thiophene HDS activity of silica supported CoMo catalysts[J]. Appl Catal A:Gen, 2002,229(1/2):261-271.
43. [43]
  GUICHARD B, AUBERGER M R, DEVERS E, LEGENS C, RAYBAUD P. Aging of Co(Ni)MoP/Al₂O₃ catalysts in working state[J]. Catal Today, 2008,130:97-108. doi: 10.1016/j.cattod.2007.09.007
44. [44]
  WALTON R A. Some remarks concerning the X-ray photoelectron spectra of the Co-Mo-Al₂O₃ hydrodesulfurization catalyst system[J]. J Catal, 1976,44(2):335-337.
45. [45]
  PAWELEC B, NAVARRO R M, MARTIN J M C, AGUDO A L, VASUDEVAN P T, FIERRO J L G. Silica-alumina-supported transition metal sulphide catalysts for deep hydrodesulphurization[J]. Catal Today, 2003,86(1/4):73-85.
46. [46]
  HAYDEN T F, DUMESIC J A. Studies of the structure of molybdenum oxide and sulfide supported on thin films of alumina[J]. J Catal, 1987,103(2):366-384. doi: 10.1016/0021-9517(87)90128-X
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Effect of ethylene glycol on the hydrogenation performance of P-doped NiMo/Al2O3 catalysts

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通讯作者: 陈斌, bchen63@163.com

Effect of ethylene glycol on the hydrogenation performance of P-doped NiMo/Al₂O₃ catalysts