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

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。

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

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.