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氧化法脱除重油催化裂化柴油中的硫化物

李瑞丽,刘 瑛,李 波   

  1. 中国石油大学(北京)重质油国家重点实验室,北京 102249
  • 出版日期:2013-08-05 发布日期:2013-08-05

Oxidative desulfurization of RFCC diesel fuel

LI Ruili,LIU Ying,LI Bo   

  1. State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249,China
  • Online:2013-08-05 Published:2013-08-05

摘要: 采用双氧水-甲酸对重油催化裂化柴油进行氧化,然后使用N,N-二甲基甲酰胺萃取剂萃取脱硫。研究了在反应体系中氧化时间、氧化温度以及双氧水与甲酸的加入量对氧化脱硫率的影响,并考察了加入分散剂Span-80的效果。最终得到双氧水-甲酸-Span-80体系最佳氧化条件:分散剂Span-80为2.0%,双氧水为36%,甲酸为32%,氧化温度为60 ℃,氧化时间为50 min。分散剂Span-80的加入可以大大提高双氧水-甲酸体系对重油催化裂化柴油的氧化脱硫能力。在双氧水-甲酸体系最佳条件下氧化萃取脱硫率为85.58%,双氧水-甲酸-Span-80体系脱硫率高达98.27%,重油催化裂化柴油的硫含量由12 500 mg/L降至216 mg/L。气相色谱结果显示,氧化脱硫后重油催化裂化柴油中的噻吩、苯并噻吩及其衍生物基本被脱除,有少量二苯并噻吩及其衍生物需要进一步脱除。

关键词: 重油催化裂化柴油, 氧化脱硫, 双氧水-甲酸, 分散剂Span-80

Abstract: Sulfur compounds of RFCC diesel oil were removed by using H2O2-formic acid as oxidant and DMF as extractant. The effects of oxidation time,oxidation temperature,H2O2 dosage and formic acid dosage on desulfurization efficiency were studied. The effect of dispersant Span-80 on desulfurization efficiency of oxidation with H2O2-formic acid were also investigated. The optimal oxidation conditions of H2O2-formic acid-Span-80 were mass fraction of Span-80 dispersant 2.0%,volume fraction of H2O2 oxidant 36%,volume fraction of formic acid 32%,oxidation temperature 60 ℃,oxidation time 50 min. Desulfurization rate was increased from 85.58% to 98.27% by Span-80 dispersant. The sulfur content of RFCC diesel fuel could be lowered from 12500 mg/L to 216 mg/L. According to GC analysis,the removals of thiophene,benzothiophene and its derivatives were almost complete,and further efforts are needed to remove dibenzothiophene and its derivatives.

Key words: RFCC diesel fuel, oxidation desulfurization, H2O2-formic acid, dispersant Span-80

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