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。
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.
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 6 562752[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. |
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