Pt/ZSM-12催化剂上费托合成馏分油的加氢异构反应
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摘要
费托合成油的硫、氮和芳烃含量很低,是新一代清洁油品的优选。采用Pt/ZSM-12催化剂,以费托合成馏分油为原料,在固定床加氢中试装置上进行加氢异构实验,考察了反应温度的影响,并对反应产物的性质及利用方案进行了研究。结果表明,随反应温度增加,柴油馏分的收率、凝固点和冷滤点均逐渐降低;结合反应生成油全馏分的组成分析可知,较高的反应温度有利于裂化反应和异构反应的进行,但反应温度过高时,对裂化反应的促进作用更明显。反应生成油中柴油馏分的十六烷指数很高、密度很低,可作为高十六烷值的车用柴油调合组分;在较高的反应温度下,轻柴油馏分段可生产替代航煤燃料,重柴油馏分仍可作为高十六烷值的车用柴油调合组分。
Fischer-Tropsch synthetic oils have low levels of sulfur, nitrogen and aromatics and are preferred for a new generation of ultraclean oils. In a hydrogenation pilot unit, the hydroisomerization of Fischer-Tropsch synthetic diesel oil over Pt/ZSM-12 catalyst under medium-pressure conditions was carried out in order to investigate the effect of temperature on the hydroisomerization and hydrocracking reaction during the process. Meanwhile, the main physical properties of the products were determined to explore their potential utilization as fuels. It was found that the yield as well as the freezing point and the cold filter plugging point of the diesel fractions in the products decreased with increasing temperature. The result including the composition of the whole fraction in the products indicated that the higher temperature was favorable for the hydroisomerization and hydrocracking reaction. However, when the temperature was too high, the promoting effect for the hydrocracking reaction was more obvious. The diesel fractions in the products were characterized by extremely high cetane index and low density compared to conventional diesel, justifying their application as the blending component of automotive diesel oil for increasing the cetane index.When the temperature was relatively high, the light diesel fraction of the product could meet the demands of the alternative jet fuel,while the heavy diesel fraction can also be used as the blending component of automotive diesel oil for increasing the cetane index.
Fischer-Tropsch synthetic oils have low levels of sulfur, nitrogen and aromatics and are preferred for a new generation of ultraclean oils. In a hydrogenation pilot unit, the hydroisomerization of Fischer-Tropsch synthetic diesel oil over Pt/ZSM-12 catalyst under medium-pressure conditions was carried out in order to investigate the effect of temperature on the hydroisomerization and hydrocracking reaction during the process. Meanwhile, the main physical properties of the products were determined to explore their potential utilization as fuels. It was found that the yield as well as the freezing point and the cold filter plugging point of the diesel fractions in the products decreased with increasing temperature. The result including the composition of the whole fraction in the products indicated that the higher temperature was favorable for the hydroisomerization and hydrocracking reaction. However, when the temperature was too high, the promoting effect for the hydrocracking reaction was more obvious. The diesel fractions in the products were characterized by extremely high cetane index and low density compared to conventional diesel, justifying their application as the blending component of automotive diesel oil for increasing the cetane index.When the temperature was relatively high, the light diesel fraction of the product could meet the demands of the alternative jet fuel,while the heavy diesel fraction can also be used as the blending component of automotive diesel oil for increasing the cetane index.
引文
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[10]刘国柱,韩立军,师亚威,等.Pt/SAPO-11催化费托合成油选择性加氢异构化制备替代喷气燃料[J].石油化工,2015,44(2):144-150.
[11]吴伟,李凌飞,武光,等.具有介孔结构的ZSM-12分子筛的制备、表征及催化性能[J].催化学报,2009,30(6)531-536.
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[14]GB19147-2016.车用柴油(V)[S].
[15]胡泽祥,李春生,周立坤,等.柴油润滑性问题的由来和研究现状[J].石油学报(石油加工),2005(01):18-25.
[16]黄勇成,周龙保,蒋德明.清洁燃料F-T柴油在柴油机中应用的研究[J].内燃机工程,2005,26(5):18-23.
[17]王凤滨,景晓军,高俊华.燃用费托柴油对国IV柴油机性能的影响[J].汽车技术,2012(10):7-10.
[18]韩立军.费托合成煤油加氢异构制替代喷气燃料[D]天津:天津大学,2012.
[19]US DOD,MIL-DTL-83133G.Turbine fuel,aviation kerosene type,JP-8(NATO F-34),NATO F-35,and JP-8+100(NATO F-37)[S].
[2]宋彩彩,刘蕾,刘宾,等.正庚烷在Ni2P/SAPO-11催化剂上的加氢异构化反应性能[J].石油炼制与化工2016,47(4):55-59.
[3]宋月芹,刘锋,康承琳,等.不同分子筛负载Pt催化剂上的正己烷异构化[J].石油学报(石油加工),2009,25(3):344-340.
[4]王文龙,韩洪晶,李金莲,等.正庚烷在Pt/SAPO-41上异构化性能研究[J].化学工程师,2012,26(5):16-19.
[5]胡云峰,王祥生,郭新闻,等.正辛烷在Pt/SAPO-41上的加氢异构化反应[J].催化学报,2004,25(2):87-88.
[6]吴伟,王瑜,张瑞,等.Pd/ZSM-22分子筛双功能催化剂的制备及其加氢异构化反应性能[J].黑龙江大学自然科学学报,2011,28(4):532-537.
[7]张瑀健,翟绪丽,付凯妹,等.短轴纳米ZSM-23的合成及异构化性能[J].高等学校化学学报,2017,38(2):231-237.
[8]毕云飞,夏国富,黄卫国,等.加氢异构化催化剂的研究-酸性能的影响[J].石油学报(石油加工),2017,33(5):873-879.
[9]Liu Y Y,Murata K,Sakanishi K.Hydroisom-erizationcracking of gasoline distillate from Fischer-Tropsch synthesis over bifunctional catalysts containing Pt and heteropolyacids[J].Fuel,2011,90(10):3056-3065.
[10]刘国柱,韩立军,师亚威,等.Pt/SAPO-11催化费托合成油选择性加氢异构化制备替代喷气燃料[J].石油化工,2015,44(2):144-150.
[11]吴伟,李凌飞,武光,等.具有介孔结构的ZSM-12分子筛的制备、表征及催化性能[J].催化学报,2009,30(6)531-536.
[12]Park K C,Ihm S K.Comparison of Pt/zeolite catalysts for n-hexadecane hydroisomerization[J].Appl Catal A,2000,203:201-209.
[13]Calemma V,Gambaro C,Parker Jr W O,et al.Middle distillates from hydrocracking of FT waxes:composition,characteristics and emission properties[J].Catal Today,2010,149:40-46.
[14]GB19147-2016.车用柴油(V)[S].
[15]胡泽祥,李春生,周立坤,等.柴油润滑性问题的由来和研究现状[J].石油学报(石油加工),2005(01):18-25.
[16]黄勇成,周龙保,蒋德明.清洁燃料F-T柴油在柴油机中应用的研究[J].内燃机工程,2005,26(5):18-23.
[17]王凤滨,景晓军,高俊华.燃用费托柴油对国IV柴油机性能的影响[J].汽车技术,2012(10):7-10.
[18]韩立军.费托合成煤油加氢异构制替代喷气燃料[D]天津:天津大学,2012.
[19]US DOD,MIL-DTL-83133G.Turbine fuel,aviation kerosene type,JP-8(NATO F-34),NATO F-35,and JP-8+100(NATO F-37)[S].