氧化铝和磷改性对非负载型催化剂结构和加氢脱硫性能的影响

doi:10.11944/j.issn.1000-0518.2016.08.150425

摘要/Abstract

摘要：

采用共沉淀法制备了Ni-Mo非负载型加氢脱硫催化剂,利用X射线粉末衍射分析(XRD)、低温N₂吸附分析(BET)、红外光谱分析(Py-IR 、FT-IR)、氢气程序升温还原(H₂-TPR)、程序升温脱附分析(NH₃-TPD)、拉曼光谱分析(LRS)和气相色谱分析(GC-PFPD)等技术手段,考察了Al₂O₃和磷对催化剂结构性能的影响。研究结果表明,Al₂O₃能够增加催化剂的孔容、孔径、比表面积,增加Lewis(L)酸酸量的同时形成了Brønsted(B)酸位。在含有Al₂O₃的催化剂中加入磷会形成Al-P-O结构,阻止NiAl₂O₄尖晶石结构的形成,减小活性组分与Al₂O₃之间的作用;同时磷能够减少四面体配位Mo物种数量,增加八面体配位Mo物种数量。催化剂具有较长的使用寿命;磷的加入使催化剂酸性由强酸性变成弱酸性,加氢脱硫活性由94%增加到99.8%。在温度280℃,压力4.0 MPa、液时空速2.0 h^-1和氢油体积比500条件下,可将催化裂化柴油中的4-甲基二苯并噻吩(4-MDBT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)和2,4,6-三甲基二苯并噻吩(2,4,6-TMDBT)深度脱除,硫含量由3950 μg/g降至7.9 μg/g。

关键词: 非负载催化剂, Ni-Mo, 加氢脱硫, 氧化铝, 磷

Abstract:

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.

Key words: unsupported catalysts, Ni-Mo, hydrodesulfurization, aluminium oxide

曾鹤, 施岩, 李鹤鸣, 王晨, 王海彦. 氧化铝和磷改性对非负载型催化剂结构和加氢脱硫性能的影响[J]. 应用化学, 2016, 33(8): 951-959.

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.

参考文献

[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]	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]	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]	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]	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]	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]	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]	Slavik K. Metallic Sulphide Catalysts, Processes for Synthesising Said Catalysts and Use Thereof:USP 6562752[P],2003-5-13.
[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]	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]	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/Al 2O3催化剂加氢脱氧性能的影响[J]. 化工进展,2005,24(12):1386-1389.
[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]	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]	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]	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]	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]	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]	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]	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]	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]	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]	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]	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]	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]	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]	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]	Marazri J A,Rajagopal S,Miranda R. Bifunctional Mechanism of Pyridine Hydrodenitrogenation[J]. J Catal,1995,156(2):255-264.
[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]	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]	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]	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]	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]	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]	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]	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]	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.