油品精制催化剂技术进展

doi:10.16085/j.issn.1000-6613.2016.06.015

摘要/Abstract

摘要： 描述了工业油品精制催化剂开发过程中所应考虑的六大要素,讨论了这些要素对催化剂性能提高的影响:包括通过各种技术调节手段,如无机助剂改性、有机助剂改性、超声辅助手段等实现对催化剂的理化性质调控,如改善酸性质、比表面积、孔结构、堆积密度等;通过这些技术手段还可调变金属-载体相互作用、活性金属的分散度和硫化度、MoS₂(WS₂)片晶长度和叠层数等,实现对催化活性中心形貌的控制;通过原材料选取及生产过程优化,降低催化剂成本;通过催化剂形态合理设计,提高催化剂体系的活性及稳定性。介绍了在工业油品精制催化剂技术进步中一些技术调节手段的应用,给出了系列商品催化剂活性进步的历程,并指出了提高催化剂性能的一些新思路,最后介绍了一些新的材料及方法在油品精制上的应用。

关键词: 油品, 催化剂, 加氢脱硫, 加氢脱氮, 活性, 工业技术, 新方法, 新材料

Abstract: Six major factors in the development process of industrial oil refining catalysts were introduced in this paper,and their influence on the catalyst performance were discussed as well as the regulations of the physicochemical properties of catalysts by means of various techniques,including using inorganic additives modification,organic additives modification,ultrasonic auxiliary means etc. to improve the acid properties,specific surface,pore structure,and bulk density etc. The interaction of the support and metal,the dispersion and curing degree of active metal,MoS₂ (WS₂) in length and number of layers of lamellae could be adjusted through these techniques,which realized the control of the morphology of catalytic activity center. Through the selection of raw materials and the optimization of the production progress,we could reduce the catalyst cost. The activity and stability of catalyst system could also be improved by rationally designing the catalyst form. The application of some technical and regulation means in the progress of industrial oil refining catalysts was introduced,then the course of improving the commercial catalyst activity was given,and some new ideas to improve the performance of catalysts was pointed out. Finally,some new materials and methods that used in oil refinery were also mentioned.

Key words: petroleum product, catalyst, hydrodesulfurization, hydrodenitrogenation, reactivity, industrial technology, new method, new material

中图分类号:

TE624

方向晨, 杨占林, 王继锋, 郭蓉. 油品精制催化剂技术进展[J]. 化工进展, 2016, 35(06): 1748-1757.

FANG Xiangchen, YANG Zhanlin, WANG Jifeng, GUO Rong. Technology progress on oil hydrofining catalysts[J]. Chemical Industry and Engineering Progree, 2016, 35(06): 1748-1757.

参考文献

[1] DUDLEY B.BP energy outlook 2035[Z/OL].2015:14 http://www.bp.com/en/global/corporate/energy-economics/energy-outlook-2035.html.
[2] TOPSØE H,CLAUSEN B S,MASSOTH F E.Hydrotreating Catalysis[M]. New York:Springer- Verlag Berlin Heidelberg,1996:31-33.
[3] 方向晨.加氢精制[M].北京:中国石化出版社,2006:30-37.
[4] 李大东.加氢处理工艺与工程[M].北京:中国石化出版社,2004.
[5] CHEN Wenbin,MAUGÉ F,VAN GESTEL J,et al.Effect of modification of the alumina acidity on the properties of supported Mo and CoMo sulfide catalysts[J].J.Catal.,2013,304:47-62.
[6] LEONOVA K A,KLIMOV O V, KOCHUBEY D I, et al.Optimal pretreatment conditions for Co-Mo hydrotreatment catalysts prepared using ethylenediamine as a chelating agent[J].Catal.Today,2014,220/221/222:327-336.
[7] 杨义,周勇,杨成敏,等.有机配体对加氢处理催化剂的影响进展[J].化工进展,2011,30(5):1008-1012.
[8] KAN Tao,WANG Hongyan,HE Hongxing,et al. Experimental study on two-stage catalytic hydroprocessing of middle-temperature coal tar to clean liquid fuels[J].Fuel,2011,90(11):3404-3409.
[9] ROEL P,MARK E B.Metal phosphides:preparation, characterization and catalytic reactivity[J].Catal.Lett.,2012,142(12):1413-1436.
[10] CHU Qi,FENG Jie,LI Wenying,et al.Synthesis of Ni/Mo/N catalyst and its application in benzene hydrogenation in the presence of thiophene[J].Chin.J.Catal, 2013,34(1):159-166.
[11] DAI Chengna,LEI Zhigang,ZHANG Jie,et al.Monolith catalysts for the alkylation of benzene with propylene [J].Chem.Eng.Sci.,2013,100:342-351.
[12] ZHANG Y,YONEYAMA Y,FUJIMOTO K,et al. A new preparation method of bimodal catalyst support and its application in Fischer-Tropsch synthesis[J].Topics in Catalysis,2003,26(1):129-137.
[13] 唐国旗,张春富,孙长山,等.活性氧化铝载体的研究进展[J].化工进展,2011,30(8):1756-1765.
[14] 许灵瑞,王继锋,杨占林,等.载体焙烧温度对MoNiP/γ-Al₂O₃加氢催化剂活性的影响[J].石油化工,2014,43(8):908-913.
[15] 顾忠华,罗来涛,夏梦君,等.TiO₂-Al₂O₃复合氧化物载体焙烧温度对Au-Pd催化剂加氢脱硫性能的影响[J].催化学报,2006,27(8):719-724.
[16] 闫翔云,季洪海,程福礼,等.焙烧温度对Al₂O₃微观结构和表面酸性的影响[J].石油炼制与化工,2011,42(11):41-45.
[17] TREJO F,RANA M S,ANCHEYTA J.CoMo/MgO-Al₂O₃ supported catalysts:an alternative approach to prepare HDS catalysts[J].Catal.Today,2008,130(2/3/4):327-336.
[18] CARATI A,FERRARIS G,GUIDOTTI M,et al.Preparation and characterization of mesoporous silica-alumina and silica titania with a narrow pore size distribution[J].Catal.Today,2003,77(4):315-323.
[19] DUCHET J C,TILLIETTE M J,CORNET D,et al.Catalytic properties of nickel molybdenum sulphide supported on zirconia[J].Catal.Today,1991,10(4):579-592.
[20] TANG Tiandi,YIN Chengyang,WANG Lifeng,et al.Good sulfur tolerance of a mesoporous beta zeolite-supported palladium catalyst in the deep hydrogenation of aromatics[J].J.Catal.,2008,257(1):125-133.
[21] FURIMSKY E.Carbons and carbon-supported catalysts in hydroprocessing[M].Cambrige,UK:RSC,2008.
[22] KOUZU M,KURIKI Y,HAMDY F,et al.Catalytic potential of carbon-supported NiMo-sulfide for ultra-deep hydrodesulfurization of diesel fuel[J].Appl.Catal. A:Gen.,2004,265(1):61-67.
[23] XU Bin,DONG Lin,FAN Yining,et al.A study on the dispersion of NiO and/or WO₃ on anatase[J].J.Catal.,2000,193(1):88-95.
[24] 孙桂大,李翠清,周志军,等.载体对负载型磷化钨催化剂性能的影响[J].石油学报(石油加工),2007,23(6):18-23.
[25] KLICPERA T,ZDRAZIL M.Preparation of high-activity MgO-supported Co-Mo and Ni-Mo sulfide hydrodesulfurization catalysts[J].J.Catal.,2002,206(2):314-320.
[26] SUN M,NICOSIA D,PRINS R.The effects of fluorine,phosphate and chelating agents on hydrotreating catalysts and catalysis[J].Catal., Today,2003,86(1/2/3/4):173-189.
[27] SUNDARAMURTHY V,DALAI A K,ADJAYE J.The effect of phosphorus on hydrotreating property of NiMo/γ-Al₂O₃ nitride catalyst[J].Appl.Catal.A:Gen.,2008,335(2):204-210.
[28] FERDOUS D,DALAI A K,ADJAYE J.A series of NiMo/Al₂O₃ catalysts containing boron and phosphorus:Part Ⅱ.Hydrodenitrogenation and hydrodesulfurization using heavy gas oil derived from Athabasca bitumen[J].Appl.Catal.A:Gen.,2004,260(2):153-162.
[29] VILLARROEL M,BAEZA P,GRACIA F,et al.Phosphorus effect on Co//Mo and Ni//Mo synergism in hydrodesulphurization catalysts[J].Appl.Catal.A:Gen.,2009,364(1/2):75-79.
[30] GRIBOVAL A,BLANCHARD P,PAYEN E,et al.Characterization and catalytic performances of hydrotreatment catalysts prepared with silicium heteropolymolybdates: comparison with phosphorus doped catalysts[J].Appl.Catal.A:Gen., 2001,217(1/2):173-183.
[31] USMA N,YAMAMOTO T,KUBOTA T,et al.Effect of phosphorus addition on the active sites of a Co-Mo/Al₂O₃ catalyst for the hydrodesulfurization of thiophene[J].Appl.Catal.A:Gen.,2007,328(2):219-225.
[32] STANISLAUS A,ABSI-HALABI M,AL-DOLOMA K.Effect of phosphorus on the acidity of γ-alumina and on the thermal stability of γ-alumina supported nickel-molybdenum hydrotreating catalysts[J].Appl.Catal.,1988,39:239-253.
[33] 周同娜,尹海亮,韩姝娜,等.磷对Ni(Co)Mo(W)/Al₂O₃加氢处理催化剂的影响研究进展[J].化工进展,2008,27(10):1581-1587.
[34] 彭卫星,王继锋,杨占林,等.磷对MoNi/γ- Al₂O₃加氢处理催化剂性能的影响[J].工业催化,2012,20(10):47-51.
[35] DAVID J,PÉREZ-MARTÍNEZ,PIERRE E,et al.Study of the selectivity in FCC naphtha hydrotreating by modifying the acid-base balance of CoMo/γ-Al₂O₃catalysts[J].Appl.Catal.A:Gen., 2010,390(1/2):59-70.
[36] SAIH Y,SEGAWA K.Catalytic activity of CoMo catalysts supported on boron-modified alumina for the hydrodesulphurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J].Appl.Catal.A: Gen., 2009,353(2):258-265.
[37] RAMIREZ J,RUIZ-RAMIREZ L,CEDENO L,et al.Titania-alumina mixed oxides as supports for molybdenum hydrotreating catalysts[J].Appl.Catal.A:Gen., 1993,93(2):163-180.
[38] THOMPSON M S.Preparation of high activity silica-supported hydrotreating catalysts and catalysts thus prepared:EP 0181035[P].1986-05-14.
[39] 李丽,金环年,胡云剑.加氢处理催化剂制备技术研究进展[J].化工进展,2013,32(7):1564-1569.
[40] 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.
[41] FUJIKAWA T,KATO M,KIMURA H,et al.Development of highly active Co-Mo catalysts with phosphorus and citric acid for ultra-deep desulfurization of diesel fractions (Part 1) preparation and performance of catalysts[J].J.Jpn.Petrol.Inst., 2005,48(2):106-113.
[42] LÉLIAS M A,VAN GESTEL J,MAUGÉ F,et al.Effect of NTA addition on the formation,structure and activity of the active phase of cobalt–molybdenum sulfide hydrotreating catalysts[J].Catal.Today,2008,130(1):109-116.
[43] KISHAN G,COULIER L,DE BEER V H J,et al.Sulfidation and thiophene hydrodesulfurization activity of nickel tungsten sulfide model catalysts,prepared without and with chelating agents[J].J.Catal., 2000,196(1):180-189.
[44] NIKULSHIN P A,MOZHAEV A V,MASLAKOV K I,et al.Genesis of HDT catalysts prepared with the use of Co₂Mo₁₀HPA and cobalt citrate:study of their gas and liquid phase sulfidation[J].Appl.Catal.B:Environ., 2014,158/159:161-174.
[45] TREJO F,RANA M S,ANCHEYTA J,et al.Hydrotreating catalysts on different supports and its acid-base properties[J].Fuel,2012,100:163-172.
[46] YU Guanglin,ZHOU Yasong,WEI Qiang,et al.A novel method for preparing well dispersed and highly sulfided NiW hydrodenitrogenation catalyst[J].Catal.Commun., 2012,23:48-53.
[47] 杨占林,彭绍忠,姜虹,等.制备技术对加氢处理催化剂性能的影响[J].石油化工,2012,41(8):885-889.
[48] 赵建宏,宋成盈,王留成.催化剂的结构与分子设计[M].北京:中国工人出版社,1998:42-56.
[49] 韩崇仁.加氢裂化工艺与工程[M].北京:中国石化出版社,2001:227.
[50] GRANGE P,VANHAEREN X.Hydrotreating catalysts,an old story with new challenges[J].Catal.Today,1997,36(4):375-391.
[51] FURIMSKY E,AMBERG C H.A comparison of the catalytic properties of(unsupported)MoS₂ and WS₂(hydrodesulfurization catalysts)[C].New Orleans:ACS,1977.
[52] DE BEER V H J,VAN SINT FIET T H M,ENGELEN J F,et al.The CoO-MoO₃-Al₂O₃ catalyst. IV. Pulse and continuous flow experiments and catalyst promotion by cobalt,nickel,zinc,and manganese[J].J.Catal.,1972,27(3):357-368.
[53] COOPER B H,DONNIS B B L,MOYSE B.Hydroprocessing conditions affect catalyst shape selection[J].Oil Gas J., 1986,84(49):39-44.
[54] 方向晨,郭蓉,杨成敏.柴油超深度加氢脱硫催化剂的开发及应用[J].催化学报,2013,34(1):130-139.
[55] 苏玉蕾,何丰,李华波.催化剂成型工艺及技术研究[J].工业催化,2013,21(4):15-20.
[56] 蒋立敬,王德会.FZC系列常压渣油加氢处理催化剂的开发及工业应用[J].工业催化,2000,8(5):52-56.
[57] 杨占林,彭绍忠,姜虹,等.蜡油加氢处理催化剂上金属杂质沉积规律研究[J].工业催化,2012,20(4):43-46.
[58] 方向晨.国内外渣油加氢处理技术发展现状及分析[J].化工进展,2011,30(1):95-104.
[59] JR TORRISI S P,FLINN N,GABRIELOV A,et al.Unlocking the potential of the ULSD unit:CENTERA is the key[C/CD]//NPRA Annual Meeting,AM-10-169.USA:Phoenix,AZ,2010.
[60] MAYO S.Experiences in maximizing performance of ULSD units[C/CD]//NPRA Annual Meeting,AM-09-14.USA:San Antonio,TX,2009.
[61] 杨占林,姜虹,唐兆吉,等.FF-56加氢裂化预处理催化剂的制备及其性能[J].石油化工,2014,43(9):1008-1013.
[62] VOGT K,LELIVELD B,MAYO S.Crossing frontiers in the performance and economic return of ULSD units[C/CD]//NPRA Annual Meeting,AM-10-170.USA:Phoenix,AZ,2010.
[63] WANG Weiyan,YANG Yunquan,BAO Jianguo,et al.Characterization and catalytic properties of Ni-Mo-B amorphous catalysts for phenol hydrodeoxygenation[J].Catal.Commun.,2009,11(2):100-105.
[64] LEE J J,KIM H,KOH J H,et al.Performance of CoMoS/Al₂O₃ prepared by sonochemical and chemical vapor deposition methods in the hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene[J].Appl.Catal.B:Environ.,2005,58(1/2):89-95.
[65] LEE S I,CHO A,KOH J H,et al.Co promotion of sonochemically prepared MoS₂/Al₂O₃ by impregnation with Co(acac)₂·2H₂O[J]. Appl.Catal.B:Environ.,2011,101(3/4):220-225.
[66] 梁新义,张黎明,丁宏远,等.超声促进浸渍法制备催化剂LaCoO₃/γ-Al₂O₃[J].物理化学学报,2003,19(7):666-669.
[67] BECK J S,VARTULI J C.Recent advances in the synthesis,characterization and applications of mesoporous molecular sieves[J].Curr.Opin.Solid State Mater.Sci.,1996,1(1):76-87.
[68] 张凯,王鼎聪.第三次纳米自组装制备大孔主客体催化材料[J].中国科学(化学),2013,43(11):1548-1556.
[69] 李思洋,赵德智,王鼎聪,等.纳米自组装大孔催化剂对催化裂化柴油的加氢催化性能[J].石油化工高等学校学报,2014,27(1):11-16.
[70] GHAMPSON I T,SEPÚLVEDAC,GARCIA R,et al.Guaiacol transformation over unsupported molybdenum-based nitride catalysts[J].Appl.Catal.A:Gen.,2012,413/414:78-84.
[71] PARK H K,KIM D S,KIM K L.Hydrodesulfurization of dibenzothiophene over supported and unsupported molybdenum carbide catalysts[J].Korean J.Chem.Eng.,1998,15(6):625-630.
[72] JUJJURI S,CRDENAS-LIZANA F,KEANE M A.Synthesis of group VI carbides and nitrides:application in catalytic hydrodechlorination[J].J.Mater.Sci.,2014,49(15):5406-5417.
[73] OYAMA S T,GOTT T,ZHAO Haiyan,et al.Transition metal phosphide hydroprocessing catalysts:a review[J].Catal.Today,2009,143(1/2):94-107.
[74] INFANTES-MOLINA A,CECILIA J A,PAWELEC B,et al.Ni₂P and CoP catalysts prepared from phosphite-type precursors for HDS-HDN competitive reactions[J].Appl.Catal.A:Gen.,2010,390(1/2):253-263.
[75] GOTT T,OYAMA S T.A general method for determining the role of spectroscopically observed species in reaction mechanisms:analysis of coverage transients(ACT)[J].J.Catal.,2009,263(2):359-371.
[76] CHOUZIER S,VRINAT M,CSERI T,et al.HDS and HDN activity of (Ni,Co)Mo binary and ternary nitrides prepared by decomposition of hexamethylenetetramine complexes[J].Appl.Catal.A:Gen., 2011,400(1/2):82-90.
[77] GEUS J W,VAN GIEZEN J C.Monoliths in catalytic oxidation[J].Catal.Today,1999,47(1/2/3/4):169-180.
[78] HAYES R E,LIU B,MOXOM R,et al.The effect of washcoat geometry on mass transfer in monolith reactors[J].Chem.Eng.Sci.,2004,59(15):3169-3181.
[79] JOSHI S Y,HAROLD M P,BALAKOTAIAH V.Low-dimensional models for real time simulations of catalytic monoliths[J].AIChE J., 2009,55(7):1771-1783.
[80] HECK R M,FARRAUTO R J.Automobile exhaust catalysts[J].Appl.Catal.A:Gen.,2001,221(1/2):443-457.
[81] 李贤,顾雄毅,何孝祥,等.乙苯CO₂脱氢规整结构催化剂[J].化工进展,2010,29(s2):189-193.
[82] 王天明,刘新斌,王志杰,等.基于结构化催化剂的低浓度甲烷流向变换催化燃烧[J].化工进展,2008,27(s1):469-472.
[83] 崔海青,邢美旺,陈光.FF-46和FC-32齿球型催化剂在馏分油加氢装置的工业应用[J].当代化工,2013,42(6):857-860.