催化裂化脱硫助剂的研究
摘要
为了共建一个“健康、安全、环保”的新环境,社会对汽柴油的要求也越来越苛刻。中国在2008年汽油硫含量标准降低到了150μg/g,欧美有些国家的汽油标准已经降低到10μg/g。然而另一方面,随着我国石油炼制工业的发展,国内原油越来越难以满足炼油工业的需要,加工进口高硫原料已成为发展的趋势。在我国,大约有80%的汽油来自于催化裂化过程,其中的硫约占商品汽油硫含量的90%。因此对于催化裂化汽油脱硫技术的研究开发,降低汽油中硫含量已经成为当务之急。
USY/ZnO/Al2O3体系脱硫效果明显,并且不会降低重油转化率,但水热条件下ZnO易于和体系中的Al反应,致使吸附脱硫活性中心和裂化脱硫中心同时失活。本文在原有助剂基础上,以自制纯硅多孔材料为载体,将ZnO装入孔道中从而使它和Al得到隔离,这样既可以使吸附硫化物的活性中心ZnO和裂化硫化物的活性中心USY都得以保护而不会相互反应,又可以保持助剂的选择性脱除硫化物的性能。在微反和固定流化床装置上对引入自制纯硅多孔材料的助剂进行评价,并且利用X射线衍射仪器(XRD)对助剂结构进行扫描。实验结果表明,自制纯硅多孔材料对ZnO和USY起到有效阻隔的作用;以兰州VGO为原料,某炼厂催化剂为平衡剂(微反活性为59),引入自制多孔材料的助剂添加量为25%时,汽油脱硫率可以达到30%以上,并且汽油选择性、烃类组成、以及汽油辛烷值没有明显变化。考察活性组分A的脱硫性能,由于A较高的L酸酸性,Al2O3/USY/A/自制多孔材料体系的脱硫效果也较好。
With development of the society, the environment which humankind lived in is required cleanner. Air pollution, caused by gasoline engine exhaust gas (SOX), is one of the most serious problems in the world, and much attention has been focused on the deeping desulfurization of gasoline. Sulfur in gasoline is not only a direct contributor to SOX emissions, it is also a poison affecting the low-temperature activity of automobile catalytic converters. Therefore, it influences volatile organic compounds, NOX, and total toxic emissions. Consequently, every country limits the content of sulfur in gasoline stringently. Sulfur content has been lower than 10μg/g in some states of the United States. In China it is reduced to 150μg/g from 300μg/g in 2008. About 90% of sulfur in gasoline originates from FCC (fluid catalytic cracking) gasoline, so reducing the sufur content of FCC gasoline is main target of sufer removal.
Several different routes to reduce the content of sulfur can be considered, but using additives for sulfur removal to reduce sulfur content of FCC gasoline during the in situ FCC process is the most economical route to desulfurization. The USY/ZnO/Al2O3 additive we developed can reduce more than 30% of sulfur in gasoline. However, the hydrothermal treatment at high temperature may cause deactivation of the additive. After the fresh additive is aged at 800℃with 100% steam, the micro-activity and sulfur removal activity drop significantly. These changes may be caused by the strong interactions between USY and ZnO. ZnO can capture the framework Al of USY to form inert ZnAl2O4 spinel and cause the collapse of the framework. When the content of ZnO in the samples is enough, ZnO can react with the Si in the collapsed framework to form Zn2SiO4 willemite. Here, we introduce a porous mass to isolate ZnO and USY, in order to depress the interactions between them. In this paper, additives for desulfurization of FCC gasoline during FCC process have been evaluated in a Confined-Fluidized-Bed reaction apparatus with Lanzhou VGO as feedstock. The results were as follows: the hydrothermal stability of additives can be improved by introducing the porous mass, but there is a optimum adding amount of porous mass in additives; The optimum mass of additive in equilibrium catalyst is 25%, and the sulfur content of gasoline can be reduced by more than 30 %,compared with only using equilibrium catalyst, while products distribution do not change obviously. Another additive sample Al2O3/USY/A/porous mass has a higher desulfurization ratio, yet products distribution change obviously.
USY/ZnO/Al2O3体系脱硫效果明显,并且不会降低重油转化率,但水热条件下ZnO易于和体系中的Al反应,致使吸附脱硫活性中心和裂化脱硫中心同时失活。本文在原有助剂基础上,以自制纯硅多孔材料为载体,将ZnO装入孔道中从而使它和Al得到隔离,这样既可以使吸附硫化物的活性中心ZnO和裂化硫化物的活性中心USY都得以保护而不会相互反应,又可以保持助剂的选择性脱除硫化物的性能。在微反和固定流化床装置上对引入自制纯硅多孔材料的助剂进行评价,并且利用X射线衍射仪器(XRD)对助剂结构进行扫描。实验结果表明,自制纯硅多孔材料对ZnO和USY起到有效阻隔的作用;以兰州VGO为原料,某炼厂催化剂为平衡剂(微反活性为59),引入自制多孔材料的助剂添加量为25%时,汽油脱硫率可以达到30%以上,并且汽油选择性、烃类组成、以及汽油辛烷值没有明显变化。考察活性组分A的脱硫性能,由于A较高的L酸酸性,Al2O3/USY/A/自制多孔材料体系的脱硫效果也较好。
With development of the society, the environment which humankind lived in is required cleanner. Air pollution, caused by gasoline engine exhaust gas (SOX), is one of the most serious problems in the world, and much attention has been focused on the deeping desulfurization of gasoline. Sulfur in gasoline is not only a direct contributor to SOX emissions, it is also a poison affecting the low-temperature activity of automobile catalytic converters. Therefore, it influences volatile organic compounds, NOX, and total toxic emissions. Consequently, every country limits the content of sulfur in gasoline stringently. Sulfur content has been lower than 10μg/g in some states of the United States. In China it is reduced to 150μg/g from 300μg/g in 2008. About 90% of sulfur in gasoline originates from FCC (fluid catalytic cracking) gasoline, so reducing the sufur content of FCC gasoline is main target of sufer removal.
Several different routes to reduce the content of sulfur can be considered, but using additives for sulfur removal to reduce sulfur content of FCC gasoline during the in situ FCC process is the most economical route to desulfurization. The USY/ZnO/Al2O3 additive we developed can reduce more than 30% of sulfur in gasoline. However, the hydrothermal treatment at high temperature may cause deactivation of the additive. After the fresh additive is aged at 800℃with 100% steam, the micro-activity and sulfur removal activity drop significantly. These changes may be caused by the strong interactions between USY and ZnO. ZnO can capture the framework Al of USY to form inert ZnAl2O4 spinel and cause the collapse of the framework. When the content of ZnO in the samples is enough, ZnO can react with the Si in the collapsed framework to form Zn2SiO4 willemite. Here, we introduce a porous mass to isolate ZnO and USY, in order to depress the interactions between them. In this paper, additives for desulfurization of FCC gasoline during FCC process have been evaluated in a Confined-Fluidized-Bed reaction apparatus with Lanzhou VGO as feedstock. The results were as follows: the hydrothermal stability of additives can be improved by introducing the porous mass, but there is a optimum adding amount of porous mass in additives; The optimum mass of additive in equilibrium catalyst is 25%, and the sulfur content of gasoline can be reduced by more than 30 %,compared with only using equilibrium catalyst, while products distribution do not change obviously. Another additive sample Al2O3/USY/A/porous mass has a higher desulfurization ratio, yet products distribution change obviously.
引文
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[10]朱根权,夏道宏,阙国和.催化裂化过程中硫化物的分布及转化规律[J].石油化工高等学校学报, 2000, 13(2): 40-44
[11]罗国华,王学勤,王祥生.焦化苯中的噻吩和乙醇在HZSM-5沸石上的反应[J].催化学报, 1998, 19(1): 53-57
[12]王祥生,罗国华. HZSM-5沸石上焦化苯的精制脱硫[J].催化学报. 1996, 17(6):530-534
[13] Richard F. Wormsbecher, Gwan Kim. Sulfur reduction in FCC gasoline[P]. US, US5376608, 1994
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[16] Laan J.V., Sughrue E.L., Dodwell G, et al. Control sulfur levels in FCC products [J]. Hydrocabon Processing, 2006,V85(2): 49-54
[17]王天普.催化裂化汽油脱硫技术进展[J].齐鲁石油化工, 2001, 29(1): 48-51
[18] Kerry L. Pock.. NPRA Annual Meeting. San Francisco. 1998. AM-98-37.
[19] Michael S. Ziebarth, Michael D. Amirldis, Rorbert H. Harding, Richard F. Wormsbecher. Composition for use in catalytic cracking to make reduced sulfur content gasoline[p]. US6036847, 2000
[20]曹锡章,宋天佑,王杏乔.无机化学[M].第三版.北京:高等教育出版社, 1994: 767-790
[21] Hynaux A., Sayag C., Suppan S., et al. Kinetic study of the deep hydrodesulfurization of dibenzothiophene over molybdenum carbide supported on a carbon black composite: Existence of two types of active sites[J]. Catalysis Today, 2007,V119:3-6
[22]闫永辉,卜欣立,尚平.吸附法脱除FCC汽油中含硫化合物的新技术[J].河北化工. 2003, 6: 5-8
[23]田龙胜,唐文成. FCC汽油溶剂抽提脱硫的研究[J].石油炼制与化工, 2001.9, 32(9): 7-9
[24] Eri Ito, J. A. Rob van Veen. On novel processes for removing sulphur from refinery streams[J]. Catalysis Today, 2006, V116: 446-460
[25]王宏伟,贺振富,田辉平. FCC汽油非临氢脱硫技术进展[J].化工进展, 2005, 24(11): 1216-1224
[26] Kilbane. Institute of Gas Technology.Mutant microoganisms useful for cleavage of organic C - S bonds[P] . US 5104801, 2001
[27]于国庆,高金森,徐春明.催化裂化加工含硫原油的技术[J].石化技术, 2004, 11(1): 58-61
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