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›› 2006, Vol. 6 ›› Issue (2): 181-185.

• 反应与分离 • 上一篇    下一篇

AlCl3-磺酸树脂催化噻吩类硫化物与异丁烯烷基化硫转移反应

徐新,罗国华,靳海波,佟泽民   

  1. 北京石油化工学院化工系
  • 出版日期:2006-04-20 发布日期:2006-04-20

Sulfur Transfer by Iso-butene Alkylation of Thiophenic Sulfur over Resin-supported AlCl3 Catalyst

XU Xin,LUO Guo-hua,JIN Hai-bo,TONG Ze-min   

  1. Dept. Chem. Eng., Beijing Inst. Petrochem. Technol.
  • Online:2006-04-20 Published:2006-04-20

摘要: 选择以噻吩的甲基取代衍生物(包括2-甲基噻吩、3-甲基噻吩及2,5-二甲基噻吩)与异丁烯的烷基化反应为模型反应,考察了经三氯化铝气相固载法改性的CT175树脂催化剂催化噻吩的甲基取代衍生物与烯烃的烷基化反应性能. 研究结果表明,负载AlCl3的CT175树脂催化剂对催化2-甲基噻吩、3-甲基噻吩及2,5-二甲基噻吩与异丁烯的烷基化硫转移反应均具有很高的活性,在80℃、常压、异丁烯(与氮气按摩尔比1:1配制的混合气)流量5.0 mL/min、液体(含模型硫化物2-甲基噻吩、3-甲基噻吩及2,5-二甲基噻吩的浓度分别为2033, 2045, 1543 mg/g的苯溶液)质量空速为2.5 h-1的条件下,上述5种模型硫化物均接近于完全转化. 对催化剂的活性稳定性进行了为期30 d的连续考察,结果表明,3种模型硫化物的烷基化转化率均高于99%,且催化剂活性未见下降趋势.

关键词: FCC汽油, 噻吩衍生物, 磺酸树脂, 固载, 三氯化铝, 烷基化, 脱硫

Abstract: Most of sulfur compounds (especially methyl-substitution derivatives of thiophene) exist in the temperature range higher than 110℃ boiling point fraction of FCC gasoline. A desulfurization method is proposed for the removal of sulfur compounds from FCC gasoline by alkylation reaction of thiophenic sulfur with olefins over acid catalysts, and the higher boiling sulfur-containing products are removed by fractional distillation. A macro-porous sulfonic resin CT175 supported AlCl3 by gas-phase immobilization was used as a catalyst for the alkylation reaction of methyl-substitution thiophenic sulfur as model sulfur compounds with iso-butene as an alkylating agent, and the AlCl3-CT175 resin catalyst showed that an excellent catalytic activity was achieved, and the thiophenic sulfur compounds (containing 2033 mg/g of 2-methylthiophene, 2045 mg/g of 3-methylthiophene and 1543 mg/g of 2,5-dimethylthiophene in benzene) were converted completely into higher boiling point multi-alkylthiophenic products under the reaction conditions of 80℃, atmospheric pressure, volume flow rate of iso-butene (iso-butene/N2 1:1, molecular ratio) 5.0 mL/min and WHSV 2.5 h-1. Simultaneously, the catalytic activity stability of AlCl3-CT175 was tested, as a result, more than 99.7% conversion rate was obtained and the alkylating activity had a good stability in the period of 700 h.

Key words: FCC gasoline, thiophenic derivative, sulfonicacid resin, immobilization, AlCl3, alkylation reaction, desulfurization