石油炼制与化工 ›› 2014, Vol. 45 ›› Issue (5): 66-71.

• 催化剂 • 上一篇    下一篇

竹炭基固体磺酸催化剂的制备及其催化合成癸二酸二丁酯性能研究

饶兰1,杨琴2,蒋文伟1   

  1. 1. 四川大学化工学院
      2. 成都惠恩精细化工有限责任公司
  • 收稿日期:2013-10-21 修回日期:2013-11-26 出版日期:2014-05-12 发布日期:2014-04-22
  • 通讯作者: 蒋文伟 E-mail:jdw0958@sina.com

PREPARATION AND PERFORMANCE OF SULFONATED CHARCOAL-BASED SOLID ACID CATALYST FOR SYNTHESIS OF DIBUTYL SEBACATE

  • Received:2013-10-21 Revised:2013-11-26 Online:2014-05-12 Published:2014-04-22

摘要: 以竹材为原料、氯磺酸为磺化剂,通过炭化-磺化法制备竹炭基固体磺酸催化剂,采用傅立叶红外光谱(FT-IR)、X射线衍射(XRD)、扫描电子显微镜仪(SEM)及热失重分析(TGA)等手段对催化剂进行表征,并将其用于催化癸二酸与正丁醇的酯化反应,考察制备条件对催化剂活性的影响。结果表明:竹炭基固体磺酸催化剂具有无定形炭结构,其热稳定性良好;合成催化剂的最佳条件为炭化温度325 ℃、炭化时间1 h、氯磺酸与竹炭配比2.5 mL/g、室温下磺化2 h,在此条件下制得的催化剂含酸量可达到1.77 mmol/g;在正丁醇与癸二酸摩尔比为3.0、反应时间为100 min、竹炭基固体磺酸催化剂用量为癸二酸质量的2.0 %、环己烷用量为3 mL的条件下,癸二酸转化率达99.14 %,重复使用4次后,癸二酸转化率仍可保持在80 %以上,说明催化剂性能稳定,具有良好的循环使用性能。

Abstract: A novel charcoal-based sulfonated solid acid was synthesized through carbonation and then sulfonation of the bamboo charcoal using chlorosulfonic acid. The esterification of sebacic acid and n-butyl alcohol was taken as the model reaction to investigate the impact of preparation parameters on the catalyst activity. Fourier transform infrared spectroscopy(FT-IR)、X-ray diffraction(XRD)、scanning electron microscope(SEM)and thermo gravimetric analysis(TGA)were used to characterize the catalyst. The results show that the charcoal-based solid acid catalyst has amorphous carbon structure and the catalyst prepared at the optimal conditions of carbonization at 325 ℃ for 1h and then sulfonation at room temperature for 2 h with acid-bamboo charcoal ratio of 2.5ml/g exhibits a higher catalytic activity. Its acid group can be reached 1.77 mmol/g. The conversion rate of sebacic acid reached 99.14 % at the following conditions: n-butyl alcohol to sebacic acid mole ratio 3.0, the amount of charcoal-based sulfonated solid acid for 2% of sebacic acid, 3 ml n-butyl alcohol, and reaction time 100min. After repeated use 4 times, sebacic acid conversion rate remains above 80%, indicating the good regeneration performance.