新型柴油加氢催化剂工艺技术及应用
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摘要
随着二次加工柴油组分比重的逐渐加大,柴油组分高硫、高氮劣质化的趋势日益显著。同时环保要求对柴油中的硫、氮含量指标要求越来越严。因此,研制开发一种适合加工劣质柴油的加氢催化剂势在必行。本课题研究了一种新型馏分油深度加氢处理催化剂的研制及工业应用,该催化剂适用于二次加工柴油的深度加氢处理过程,特别适用于劣质柴油(例如:高硫环烷基直馏柴油、焦化柴油、催化裂化柴油或以上柴油的混合物)的深度加氢处理,处理后的柴油可以作为优质柴油的调和组分。该加氢精制催化剂(FDS)的担体是由烷基铝或烷氧基铝水解法制成的纯度大于70%的一水铝石、与经阳离子交换的沸石混合后高温焙烧得到的复合型载体。活性组分由磷以及镍、钼构成,各组份含量(以催化剂为基准,质量含量)为:氧化镍2.5～8.0%,氧化钼10～30%,磷0.2～4.0%,其余是复合型载体。该新型催化剂工业应用取得了良好的经济效益和社会效益。主要研究结论如下:(1)FDS柴油加氢精制催化剂具有优良的加氢脱硫、加氢脱氮和加氢脱芳性能,并且具有良好的活性和稳定性,可以满足满足国III乃至国IV清洁柴油生产的要求;(2)FDS柴油加氢催化剂的制造成本低于目前同类型催化剂的制造成本;(3)工业应用结果表明,FDS柴油加氢精制催化剂及工艺技术对劣质柴油的加氢精制性能良好,整体性能超过了国内目前最好的柴油加氢催化剂;(4)随着劣质原油加工量及清洁柴油国家标准的逐渐提高,清洁柴油生产技术的需求日益紧迫,建议积极推广FDS柴油加氢精制催化剂及工艺技术,提高我国清洁柴油生产的技术水平。
With gradually raising of the secondary operation for diesel components, it becomes more noticeable that the quality of the components is increasingly poor, such as high-sulfur, high-nitrogen, and so on. At the same time, environmental indicators for sulfur and nitrogen in diesel fuel are more and more strict. Therefore, it is so imperative to search applicable hydrogenation catalyst for processing low-grade diesel. The study reports a novel catalyst for deep hydrogenation, which is suitable for hydrogenation of the secondary-processing diesel oil, especially for low-grade diesel, such as high-sulfur straight-run naphthenic diesel, coking diesel, catalytic cracking diesel oil and the mixtures of them, and so on. The diesel can be blending components of the high-quality diesel fuel after the process. The supporter of hydrotreating catalyst (FDS) is mixed high-temperature calcined carriers of diasporite by hydrolysis of alkyl aluminum or alkoxy aluminum and zeolite by cation exchange. The active component of hydrotreating catalyst (FDS) catalyst is the composition of phosphorus, nickel and molybdenum. The novel catalyst achieves good economic and social benefit for industrial applications. The conclusions are as follows: (1) FDS diesel hydrotreating catalysts perform well in hydrodesulfurization, hydrodenitrogenation and hydrodearomatization, which meet the III and IV of national standard for clean diesel production, with good activity and stability. (2)The cost of FDS diesel hydrotreating catalysts is lower than the current catalyst of the same type. (3) The industrial application results show that, FDS diesel hydrotreating catalyst performs well in hydrotreating low-grade diesel fuel, the overall performance of which exceeds current domestic diesel hydrogenation catalyst. (4) With scale-up processing of low-quality crude oil and improvement of national standards for clean diesel, the demand for clean diesel production technology is increasingly urgent. So it is recommended to promote the FDS diesel hydrotreating catalyst to improve the production of clean diesel technology.
With gradually raising of the secondary operation for diesel components, it becomes more noticeable that the quality of the components is increasingly poor, such as high-sulfur, high-nitrogen, and so on. At the same time, environmental indicators for sulfur and nitrogen in diesel fuel are more and more strict. Therefore, it is so imperative to search applicable hydrogenation catalyst for processing low-grade diesel. The study reports a novel catalyst for deep hydrogenation, which is suitable for hydrogenation of the secondary-processing diesel oil, especially for low-grade diesel, such as high-sulfur straight-run naphthenic diesel, coking diesel, catalytic cracking diesel oil and the mixtures of them, and so on. The diesel can be blending components of the high-quality diesel fuel after the process. The supporter of hydrotreating catalyst (FDS) is mixed high-temperature calcined carriers of diasporite by hydrolysis of alkyl aluminum or alkoxy aluminum and zeolite by cation exchange. The active component of hydrotreating catalyst (FDS) catalyst is the composition of phosphorus, nickel and molybdenum. The novel catalyst achieves good economic and social benefit for industrial applications. The conclusions are as follows: (1) FDS diesel hydrotreating catalysts perform well in hydrodesulfurization, hydrodenitrogenation and hydrodearomatization, which meet the III and IV of national standard for clean diesel production, with good activity and stability. (2)The cost of FDS diesel hydrotreating catalysts is lower than the current catalyst of the same type. (3) The industrial application results show that, FDS diesel hydrotreating catalyst performs well in hydrotreating low-grade diesel fuel, the overall performance of which exceeds current domestic diesel hydrogenation catalyst. (4) With scale-up processing of low-quality crude oil and improvement of national standards for clean diesel, the demand for clean diesel production technology is increasingly urgent. So it is recommended to promote the FDS diesel hydrotreating catalyst to improve the production of clean diesel technology.
引文
[1] Song Chunshan, Ma Xiao liang. New design approaches to ultra-clean diesel fuels by deep desulfurization and deep dearomatization[J]. Appl Catal B: Environmental, 2003, 41: 207-238
[2] Romanow S. Gasoline and diesel sulfur content review[J]. Hydrocarb Process, 2000, 79(9): 17-19
[3]左东华,谢玉萍、聂红等,4,6-二甲基二苯并噻吩甲基脱硫反应机理的研究I.NiW体系催化剂的催化行为[J].化工学报.23(3):271-275
[4]李永安,炼油生产过程硫的分布追踪与平衡[J],石油化工腐蚀与防腐,2006,18(4): 35-38
[5]李大东,加氢处理工艺与工程[M],北京:中国石化出版社,2004:93
[6]王雪松,柴油脱硫的机理研究以及反应中的溶剂效应[J],广州化学,2007,32(1):62-66
[7] Houalla M, Nag N K, Sapre A V, et al. Hydrodesulfurization of dib enzothiophene catalyzed by sulided Co-Mo/-Al2O3: the reactionnetwork[J]. AIChE Journal, 1978, 24(6): 1015-1021
[8]龚树文,陈皓侃,李文等,负载β-Mo2N0.78催化剂上加氢脱硫和加氢脱氮反应行为的研究[J],燃料化学学报,2005,33(1):24-27
[9]柴永明,赵会吉,刘晨光.硫化型M .基加氢催化剂的制备及对二苯并唆吩的加氢脱硫性能十二届全国催化学术会议论文集,北京:2 0 04 . 3 0 9 ~ 3 11
[10]柴永明,相春娥,孔会清等,馏分油浆态床加氢处理研究:II FCC柴油加氢工艺条件及动力学研究[J],燃料化学学报,2009,37(1):53-57
[11]马丽,张登前,万国赋等,清洁柴油超深度加氢脱硫研究进展[J],工业催化,2004,14(增刊):1-2
[12]刘大鹏,李永丹,加氢脱氮催化研究的新进展[J],化工进展,2006,18(4):417-428
[13] Kasztelan S, Des Courieres T, Breysse M, et al. Hydrodenitrogenation of petroleum distillates: industrial aspects[J]. Catal Today, 1991, 10(4): 433-445
[14] Ho T C. Hydrodenitrogenation catalysts[J]. Catal Rev-Sci Eng, 1988, 30: 117-160
[15] Katzer J R, Sivasubramanian R. Procese and catalyst needs for hydrodenitrogenation[J]. Catal Rev-Sci Eng, 1979, 20(2): 155-208
[16] Perot G. The reactions involved in hydrodenitrogenation[J]. Catal Today, 1991,10(4):447-472
[17] March J. Advanced organic chemistry: reactions, mechanisms and structure, 4th-ed[M]. Singapore: John Wiley&Sons, 2001
[18] Nelson N, Levy R B. The organic chemistry of hydrodenitrogenation[J]. J Catal, 1979, 58 (3): 485-488
[19] Portefaix J L, Cattenot M, Guerriche M, et al. Conversion of saturated cyclic and noncyclic amines over a sulphided NiMo/Al2O3 catalysts: mechanisms of carbon-nitrogen bond cleavage[J]. Catal Today, 1991, 10 (4): 473-487
[20] Cattenot M, Portefaix J L, Afonso J, et al. Mechanism of carbon-nitrogen bond scission on unsupported transition metal sulfides[J]. J Catal, 1998, 173(2): 366-373
[21]林世雄,石油炼制工程(第2版)[M],北京:石油工业出版社,1988
[22]李淑培,石油加工工艺(中册)[M],北京:中国石化出版社,1999
[23]廖健,张兵,刘伯华,国外清洁燃料生产技术[J],当代石油石化,2001,9(3):28-32
[24]赵野,张文成,郭金涛等,清洁柴油的加氢技术进展[J],工业催化,2008,16(1): 10-11
[25]艾中秋,国外生产清洁柴油的加氢工艺及催化剂[J],石化技术与应用,2006,24(1):60-62
[26]袁利剑,袁大辉,张婧元,国外清洁柴油加氢催化剂的工艺进展[J],炼油与化工,2009,20(2):1-4
[27]于淼,郭蓉,王刚,国外柴油加氢脱硫催化剂的研究进展[J],当代化工,2008,37(6): 624-626
[28]赵野,申宝剑,高金森,柴油脱硫技术评述[J],精细石油化工进展,2005,6(10):49-54
[29]苏栋根,国外石油炼制催化剂的技术进展[J],工业催化,2001,9(2):3-9
[30]钱伯章,生产清洁汽柴油燃料脱硫工艺的进展[J],天然气与石油,2002,20(3):28-31
[31]朱金玲,王甫村,王俊峰等,生产低硫柴油技术的新进展[J],化工科技市场,2004,8:1-4
[32]张登前,段爱军,赵震等,加氢脱氮催化剂及反应机理研究进展[J],现代化工,2007,27(增刊):54-59
[33]柳广厦,深度加氢脱硫催化剂KF757的工业应用与条件优化[D],大连理工大学,2007: 54-57
[34]牛国兴,陈海鹰,李全芝.氟硅酸铵处理对Al2O3负载NiW催化剂性质的影响[ J] .催化学报, 1997, ( 7) : 279-283.
[35]程昌瑞,朱华青,高志贤,等.重油加氢脱氮催化剂的研制钼镍磷催化剂的制备与评价[ A] .石油炼制与化工编辑部编.加氢技术[ C] .北京:中国石化出版社, 2000. 315- 318.
[36]孙万付,马波,陈平,等. W-Ni/ Al2O3-USY催化剂中USY的作用[ J] .催化学报, 1998, ( 9) : 415- 418.
[2] Romanow S. Gasoline and diesel sulfur content review[J]. Hydrocarb Process, 2000, 79(9): 17-19
[3]左东华,谢玉萍、聂红等,4,6-二甲基二苯并噻吩甲基脱硫反应机理的研究I.NiW体系催化剂的催化行为[J].化工学报.23(3):271-275
[4]李永安,炼油生产过程硫的分布追踪与平衡[J],石油化工腐蚀与防腐,2006,18(4): 35-38
[5]李大东,加氢处理工艺与工程[M],北京:中国石化出版社,2004:93
[6]王雪松,柴油脱硫的机理研究以及反应中的溶剂效应[J],广州化学,2007,32(1):62-66
[7] Houalla M, Nag N K, Sapre A V, et al. Hydrodesulfurization of dib enzothiophene catalyzed by sulided Co-Mo/-Al2O3: the reactionnetwork[J]. AIChE Journal, 1978, 24(6): 1015-1021
[8]龚树文,陈皓侃,李文等,负载β-Mo2N0.78催化剂上加氢脱硫和加氢脱氮反应行为的研究[J],燃料化学学报,2005,33(1):24-27
[9]柴永明,赵会吉,刘晨光.硫化型M .基加氢催化剂的制备及对二苯并唆吩的加氢脱硫性能十二届全国催化学术会议论文集,北京:2 0 04 . 3 0 9 ~ 3 11
[10]柴永明,相春娥,孔会清等,馏分油浆态床加氢处理研究:II FCC柴油加氢工艺条件及动力学研究[J],燃料化学学报,2009,37(1):53-57
[11]马丽,张登前,万国赋等,清洁柴油超深度加氢脱硫研究进展[J],工业催化,2004,14(增刊):1-2
[12]刘大鹏,李永丹,加氢脱氮催化研究的新进展[J],化工进展,2006,18(4):417-428
[13] Kasztelan S, Des Courieres T, Breysse M, et al. Hydrodenitrogenation of petroleum distillates: industrial aspects[J]. Catal Today, 1991, 10(4): 433-445
[14] Ho T C. Hydrodenitrogenation catalysts[J]. Catal Rev-Sci Eng, 1988, 30: 117-160
[15] Katzer J R, Sivasubramanian R. Procese and catalyst needs for hydrodenitrogenation[J]. Catal Rev-Sci Eng, 1979, 20(2): 155-208
[16] Perot G. The reactions involved in hydrodenitrogenation[J]. Catal Today, 1991,10(4):447-472
[17] March J. Advanced organic chemistry: reactions, mechanisms and structure, 4th-ed[M]. Singapore: John Wiley&Sons, 2001
[18] Nelson N, Levy R B. The organic chemistry of hydrodenitrogenation[J]. J Catal, 1979, 58 (3): 485-488
[19] Portefaix J L, Cattenot M, Guerriche M, et al. Conversion of saturated cyclic and noncyclic amines over a sulphided NiMo/Al2O3 catalysts: mechanisms of carbon-nitrogen bond cleavage[J]. Catal Today, 1991, 10 (4): 473-487
[20] Cattenot M, Portefaix J L, Afonso J, et al. Mechanism of carbon-nitrogen bond scission on unsupported transition metal sulfides[J]. J Catal, 1998, 173(2): 366-373
[21]林世雄,石油炼制工程(第2版)[M],北京:石油工业出版社,1988
[22]李淑培,石油加工工艺(中册)[M],北京:中国石化出版社,1999
[23]廖健,张兵,刘伯华,国外清洁燃料生产技术[J],当代石油石化,2001,9(3):28-32
[24]赵野,张文成,郭金涛等,清洁柴油的加氢技术进展[J],工业催化,2008,16(1): 10-11
[25]艾中秋,国外生产清洁柴油的加氢工艺及催化剂[J],石化技术与应用,2006,24(1):60-62
[26]袁利剑,袁大辉,张婧元,国外清洁柴油加氢催化剂的工艺进展[J],炼油与化工,2009,20(2):1-4
[27]于淼,郭蓉,王刚,国外柴油加氢脱硫催化剂的研究进展[J],当代化工,2008,37(6): 624-626
[28]赵野,申宝剑,高金森,柴油脱硫技术评述[J],精细石油化工进展,2005,6(10):49-54
[29]苏栋根,国外石油炼制催化剂的技术进展[J],工业催化,2001,9(2):3-9
[30]钱伯章,生产清洁汽柴油燃料脱硫工艺的进展[J],天然气与石油,2002,20(3):28-31
[31]朱金玲,王甫村,王俊峰等,生产低硫柴油技术的新进展[J],化工科技市场,2004,8:1-4
[32]张登前,段爱军,赵震等,加氢脱氮催化剂及反应机理研究进展[J],现代化工,2007,27(增刊):54-59
[33]柳广厦,深度加氢脱硫催化剂KF757的工业应用与条件优化[D],大连理工大学,2007: 54-57
[34]牛国兴,陈海鹰,李全芝.氟硅酸铵处理对Al2O3负载NiW催化剂性质的影响[ J] .催化学报, 1997, ( 7) : 279-283.
[35]程昌瑞,朱华青,高志贤,等.重油加氢脱氮催化剂的研制钼镍磷催化剂的制备与评价[ A] .石油炼制与化工编辑部编.加氢技术[ C] .北京:中国石化出版社, 2000. 315- 318.
[36]孙万付,马波,陈平,等. W-Ni/ Al2O3-USY催化剂中USY的作用[ J] .催化学报, 1998, ( 9) : 415- 418.