Citation: ZENG He, SHI Yan, LI Heming, WANG Chen, WANG Haiyan. Effect of Aluminium Oxide and Phosphorus Modification on Structure and Hydrodesulfurization Performance of Unsupported Catalysts[J]. Chinese Journal of Applied Chemistry, ;2016, 33(8): 951-959. doi: 10.11944/j.issn.1000-0518.2016.08.150425 shu

Effect of Aluminium Oxide and Phosphorus Modification on Structure and Hydrodesulfurization Performance of Unsupported Catalysts

1.
Chemical Industry and Environment Department of Petrochemical College, Liaoning University of Petroleum Chemical Industry, Fushun, Liaoning 113001, China

Corresponding author: WANG Haiyan,
Received Date: 1 December 2015
Available Online: 4 March 2016
Fund Project:

Unsupported Ni-Mo hydrodesulfurization catalysts were prepared by a coprecipitation method and characterized by X-ray diffraction(XRD), nitrogen physisorption measurement(BET), infrared spectroscopy(Py-IR, FI-IR), H₂-temperaure programmed reduction(H₂-TPR), temperature-programmed desorption of NH₃(NH₃-TPD), Laser Raman spectroscopy(LRS) and gas chromatography analysis(GC-PFPD) tests. The effects of Al₂O₃ and phosphorus addition on the structure of the catalysts were studied. The results indicate that the addition of Al₂O₃ greatly increases the pore diameter, specific surface area, the amount of the L acid sites and also promotes the formation of B acid sites. Addition of phosphorus leads to the formation of the Al-P-O structure instead of the NiAl₂O₄ structure, and weakens the interaction between active phase and Al₂O₃. The amount of tetrahedral Mo species decreases while the anount of octahedral Mo species increases. The catalysts has a longer service life. The catalyst acidity is changed from strong to weak by adding phosphorus. The hydrodesulfurization rate is increased from 94% to 99.8%. At 280 ℃, hydrogen pressure of 4 MPa, liquid hourly space velocity(LHSV) of 1.5 h^-1 and hydrogen-to-oil volume ratio of 500, 4-methyldibenzothiophene, 4,6-dimethyldibenzothiophene and 2,4,6-trimethyldibenzothiophene catalytic cracking are depthly removed in fluid catalytic cracking diesel oil; the sulphur concentration is decreased from 3950 μg/g to 7.9 μg/g.
- unsupported catalysts,
- Ni-Mo,
- hydrodesulfurization,
- aluminium oxide,
1. [1]
  [1] Plantenga F L,Cefortain R,Eusbouts S,et al. A Hydroprocessing Catalysts with Breakthrough Acfivity[J]. Stud Surf Sci Catal,2003,145(8):407-410.
2. [2]
  [2] LI He,YIN Changlong,ZHAO Leiyan,et al. Progresses in Unsupported Hydrotreating Catalysts[J]. Petrochem Technol,2013,42(7):811-817(in Chinese).李贺,殷长龙,赵蕾艳,等. 非负载型加氢精制催化剂的研究进展[J]. 石油化工,2013,42(7):811-817.
3. [3]
  [3] Bocarando J,Huirache-Acun R,Bensch W,et al, Unsupported Ni-Mo-W Sulphide HDS Catalysts with the Varying Nickel Voncentration[J]. Appl Catal A:Gen,2009,363(2):45-51.
4. [4]
  [4] Yoosuk B,Kim J H,Song C S,et al. Highly Active MoS₂, CoMoS₂ and NiMoS₂ Unsupported Catalysts Prepared by Hydrothermal Synthesis for Hydrodesulfurization of 4,6-Dimethyldibenzothiophene[J]. Catal Today,2008,130(1):14-23.
5. [5]
  [5] Eijsbouts S,Mayo W,Fujita K. Unsupported Transition Metal Sulfide Catalysts:From Fundamentals to Industrial Application[J]. Appl Catal,A:Gen,2007,322(6):58-66.
6. [6]
  [6] Mahdavi V,Peyrovi M,Islami M,et al. Synthesis of Higher Alcohols from Syngas over Cu-Co₂O₃/ZnO-Al₂O₃ Catalyst[J]. Appl Catal,A:Gen,2005,281(1):259-265.
7. [7]
  [7] LIU Huan,YIN Changlong,ZHAO Leiyan,et al. Hydrothermal Synthesis of Ni-Mo Unsupported Catalyst and Their Catalytic Performance[J]. Pet Process Petrochem,2013,44(9):19-23(in Chinese).刘欢,殷长龙,赵蕾艳,等. 水热法合成Ni-Mo非负载型催化剂及催化加氢性能[J]. 石油炼制与化工,2013,44(9):19-23.
8. [8]
  [8] Slavik K. Metallic Sulphide Catalysts, Processes for Synthesising Said Catalysts and Use Thereof:USP 6 562752[P],2003-5-13.
9. [9]
  [9] Sun M Y,Bürgi T,Cattaneo R,et al. TPS, XPS, QEXAFS, and XANES Investigation of the Sulfidation of NiW/Al₂O₃-F Catalysts[J]. J Catal,2001,201(2):258-269.
10. [10]
  [10] Heirem J M,Reyes J,Roquero P,et al. New Hydrotreating Ni-Mo Catalysts Supported on MCM-41 Modified with Phosphorus[J]. Micropor Mesopor Mater,2005,83(1/3):283-291.
11. [11]
  [11] YANG Jun,CHEN Manying,REN Jie. Effect of Mo, W Addition on Performance of Ni/Al₂O₃ Catalyst for Hydrodeoxygenation[J]. Chem Eng Prog,2005,24(12):1386-1389(in Chinese).杨俊,陈满英,任杰. Mo,W对Ni/Al₂O₃催化剂加氢脱氧性能的影响[J]. 化工进展,2005,24(12):1386-1389.
12. [12]
  [12] Bendezú S,Cid R,Fierro J L G,et al. Thiophene Hydrodesulfurization on Sulfided Ni, W and NiW/USY Zeolite Catalysts: Effect of the Preparation Method[J]. Appl Catal,A,2000,197(197):47-60.
13. [13]
  [13] Bataillea F,Lemberton J L,Michauda P,et al. Alkyldibenzothiophenes Hydrodesulfurization-promoter Effect, Reactivity, and Reaction Mechanism[J]. J Catal,2000,191(9):409-422.
14. [14]
  [14] HU Dawei,YANG Qinghe,SUN Shuling,et al. Effect of Phosphirus on the Performance and Active Component Structure of MoCoNi/Al₂O₃ Catalyst[J]. Pet Process Petrochem,2011,42(5):1-4(in Chinese).胡大为,杨清河,孙淑玲,等. 磷对Mo-W催化剂性能及活性结构的影响[J]. 石油炼制与化工,2011,42(5):1-4.
15. [15]
  [15] Sigurdson S,Sundammurthy V,Dalai A K,et al. Phosphorus Promoted Trimetallic NiMoW/Al₂O₃, Sulfide Catalysts in Gas Oil Hydrotreating[J]. Catal,A:Chem,2008,291(1/2):30-37.
16. [16]
  [16] LI He,YIN Changlong,BAI Zhenjiang,et al. Progresses in Phosphorous Hydrotreating Catalysts[J]. Petrochem Technol,2013,42(12):1398-1404(in Chinese).李贺,殷长龙,白振江,等. 含磷加氢精制催化剂的研究进展[J]. 石油化工,2013,42(12):1398-1404.
17. [17]
  [17] SUN Yanyao,LI Fengyan,LI Qingjie,et al. Effect of Phosphorus Content on the Performance of MoP/ γ-Al₂O₃ Catalyst[J]. Pet Process Petrochem,2008,39(8):46-49(in Chinese).孙艳药,李凤艳,李庆杰,等. 磷含量对负载型磷化钼催化剂性能的影响[J]. 石油炼制与化工,2008,39(8):46-49.
18. [18]
  [18] Michaud P,Lemberton J L,Perot G. Hydrodesulfurization of Dibenzothiophene and 4,6-Dimethyldibenzo-thiophene:Effect of an Acid Component on the Activity of a Sulfided NiMo on Alumina Catalyst[J]. Appl Catal,A:Gen,1998,169(9):343-353.
19. [19]
  [19] Rana M S,Ancheyta J,Rayo P,et al. Effect of Alumina Preparation on Hydrodemetallization and Hydrodesulfurization of Maya Crude[J]. Catal Today,2004,98(98):151-160.
20. [20]
  [20] Pablo T M,Ramirez J,Cuevas R. Hydrodesulfurization of 4,6-DMDBT on NiMo and CoMo Catalysts Supported on B₂O₃-Al₂O₃[J]. Catal Today,2005,107(44):551-558.
21. [21]
  [21] YANG Xiyao. Technology of Temperature Programmed Analysis II[J]. Petrochem Technol,2002,31(1):63-73(in Chinese).杨锡尧. 程序升温分析技术(下)[J]. 石油化工,2002,31(1):63-73.
22. [22]
  [22] Ma X L,Sakanishi K,Mochida I. Hydrodesulfunzation Reactivities of Various Sulfur Compounds in Diesel Fuel[J]. Ind Eng Chem Res,1994,33(2):218-222.
23. [23]
  [23] LI Dadong. Hydrotreating Technology and Engineering[M]. Beijing:China Petrochemical Press,2004:648-650(in Chinese).李大东. 加氢处理工艺与工程[M]. 北京:中国石化出版社,2004:648-650.
24. [24]
  [24] Wang W Y,Yang Y Q,Bao J G,et al. Characterization and Catalytic Properties of Ni-Mo-B Amorphous Catalysts for Phenol Hydrodeoxygenation[J]. Catal Commun,2009,11(2):100-105.
25. [25]
  [25] Qian E W,Abe S,Kagawa Y,et al. Hydrodenitrogenation of Porphyrin on Ni-Mo Based Catalysts[J]. Chinese J Catal,2013,34(1):152-158.
26. [26]
  [26] Erdem B,Erdem S,Öksüzoğlu R M,et al. High-surface-area SBA-15-SO₃H with Enhanced Catalytic Activity by the Addition of Poly(ethylene glycol)[J]. J Por Mater,2013,20(5):1041-1049.
27. [27]
  [27] Marazri J A,Rajagopal S,Miranda R. Bifunctional Mechanism of Pyridine Hydrodenitrogenation[J]. J Catal,1995,156(2):255-264.
28. [28]
  [28] Vakros J,Lycourghiotis A,Voyiatzis G A,et al. CoMo/Al₂O₃-SiO₂ Catalysts Prepared by Co-equilibrium Deposition Filtration:Characterization and Catalytic Behavior for the Hydrodesulphurization of Thiophene[J]. Appl Catal B:Environ,2010,96(3/4):496-507.
29. [29]
  [29] ZHOU Tongna,YIN Hailiang,LIU Yunqi. Effect of Phosphorus Content on the Active Phase Structure of Ni-Mo/γ-Al₂O₃ Catalyst[J]. J Fuel Chem Technol,2010,38(1):70-74(in Chinese).周同娜,尹海亮,柳云骐. 磷含量对NiMo/γ-Al₂O₃催化剂活性相结构的影响[J]. 燃料化学学报,2010,38(1):70-74.
30. [30]
  [30] YANG Zhanlin,PENG Shaozhong,LIU Xueling,et al. Effects of Phosphorus Modification on Structure and Properties of Mo-Ni/γ-Al₂O₃ Catalyst[J]. Petrochem Technol,2007,36(8):784-788(in Chinese).杨占林,彭绍忠,刘雪玲,等. P改性对Mo-Ni/γ-Al₂O₃催化剂结构和性质的影响[J]. 石油化工,2007,36(8):784-788.
31. [31]
  [31] CAO Guangwei,LUO Xihui,LIU Zhenhua,et al. Preparation and Characterization of Hydrotreating Catalysts I.Preparation of MoNiP/Al₂O₃ and Effect of Promoters[J]. Chinese J Catal,2001,22(2):143-147(in Chinese).曹光伟,罗锡辉,刘振华,等. 加氢处理催化剂的制备与表征I MoNiP/Al₂O₃催化剂的制备及助剂的作用[J]. 催化学报,2001,22(2):143-147.
32. [32]
  [32] YUAN Hui,XU Guangtong,QI Herima,et al. Application of Laser Raman Spectroscopy in the Co-Mo/Al₂O₃ Hydrogenation Catalyst[J]. Spectrosc Spectr Anal,2013,34(2):435-438(in Chinese).袁蕙,徐广通,齐和日玛,等. 激光拉曼光谱在加氢脱硫催化剂Co-Mo/Al₂O₃中的应用研究[J]. 光谱学与光谱分析,2013,34(2):435-438.
33. [33]
  [33] Bergwerff J A,Jansen M,Leliveld B G,et al. Influence of the Preparation Method on the Hydrotreating Activity of MoS₂/Al₂O₃ Extrudates:A Raman Microspectroscopy Study on the Genesis of the Active Phase[J]. J Catal,2006,243(2):292-302.
34. [34]
  [34] Van de Water L G A,Bergwerff J A,Leliveld B G,et al. Insights into the Preparation of Supported Catalysts:A Spatially Resolved Raman and UV-Vis Spectroscopic Study into the Drying Process of CoMo/γ-Al₂O₃ Catalyst Bodies[J]. J Phys Chem B,2005,109(30):14513-14522.
35. [35]
  [35] Al-Megren H A,González-Cortés S L,Xiao Tiancun,et al. A Comparative Study of the Catalytic Performance of Co-Mo and Co(Ni)-W Carbide Catalysts in the Hydrodenitrogenation(HDN) Reaction of Pyridine[J]. Appl Catal A:Gen,2007,329(10):36-45.
36. [36]
  [36] ZHAO Leiyan,YIN Changlong,LIU Huan,et al. Study on Hydrodesulfurization Process of Diesel on Unsupported Catalyst[J]. Pet Process Petrochem,2014,44(10):39-43(in Chinese).赵蕾艳,殷长龙,刘欢,等. 非负载型催化剂上柴油深度加氢脱硫工艺条件研究[J]. 石油炼制与化工,2014,44(10):39-43.
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