催化学报 ›› 2011, Vol. 32 ›› Issue (11): 1755-1761.DOI: 10.3724/SP.J.1088.2011.10711

• 研究论文 • 上一篇    下一篇

基于纤维素的固体酸催化剂的制备及其催化高酸值废油脂生产生物柴油

娄文勇 1,2,a, 蔡俊 2, 段章群 1, 宗敏华 1,b   

  1. 1华南理工大学轻工与食品学院, 广东广州 510640; 2湖北工业大学发酵工程省部共建教育部重点实验室, 湖北武汉 430068
  • 收稿日期:2011-07-20 修回日期:2011-09-05 出版日期:2011-11-14 发布日期:2015-03-30

Preparation of Cellulose-Derived Solid Acid Catalyst and Its Use for Production of Biodiesel from Waste Oils with High Acid Value

LOU Wenyong1,2,a, CAI Jun2, DUAN Zhangqun1, ZONG Minhua1,b   

  1. 1College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, Guangdong, China; 2Key Laboratory of Fermentation Engineering (Ministry of Education), Hubei University of Technology, Wuhan 430068, Hubei, China
  • Received:2011-07-20 Revised:2011-09-05 Online:2011-11-14 Published:2015-03-30

摘要: 以廉价的纤维素为原料, 经不完全炭化和磺化制得含高密度 (1.69 mmol/g) SO3H 基团的固体酸催化剂 Cellulose-SO3H. 结果表明, 该催化剂适宜的制备条件为: 在 400 oC 炭化 15 h, 再在 150 oC 磺化 15 h. 所得催化剂在油酸与甲醇的酯化反应中表现出明显高于其它几种典型固体酸催化剂 (铌酸, Amberlyst-15, 硫酸化氧化锆) 的活性, 同时还能高效地催化棕榈酸或硬脂酸以及高酸值废油脂 (较多脂肪酸) 与甲醇的酯化反应. 在醇/油摩尔比为 25, 催化剂用量为 10% (基于废油脂的质量), 于 85 °C 反应 10 h 的条件下, 生物柴油收率约为 95%, 明显高于上述三种典型固体酸催化剂. 连续使用 30 批次 (每批次 10 h) 后, Cel-lulose-SO3H 仍能保持初始催化活性的 90% 以上, 表现出极好的操作稳定性. 可见, 所制 Cellulose-SO3H 催化剂在生物柴油领域具有较好的应用潜力.

关键词: 纤维素, 固体酸催化剂, 生物柴油, 酯化, 废油脂

Abstract: A cheap cellulose-derived solid acid catalyst (Cellulose-SO3H), containing SO3H groups (1.69 mmol/g), was successfully prepared through sulfonation of incompletely carbonized cellulose. Various preparation variables exerted remarkable effects on the catalytic activity of the prepared catalyst, and the optimal preparation conditions were found as follows: carbonization at 400 oC for 15 h and subsequent sulfonation at 150 oC for 15 h. The resulting catalyst showed significantly higher activity for esterification of oleic acid with methanol than several typical solid acid catalysts (niobic acid, amberlyst-15, and sulfated zirconia). The Cellulose-SO3H catalyst was capable of efficiently catalyzing esterification of other higher fatty acids (palmitic acid and stearic acid) with methanol to the corresponding fatty acid methyl esters (biodiesel). Moreover, the conversion of waste oils containing 27.8% free fatty acids to biodiesel catalyzed by Cellulose-SO3H was investigated. It was found that the optimal molar ratio of methanol to oil, catalyst amount, reaction temperature, and reaction time were 25, 10% (based on the mass of waste oil), 85 °C, and 10 h, respectively. Under the optimal reaction conditions, the yield of biodiesel obtained catalyzed by Cellulose-SO3H was much higher than that by the above-mentioned three typical catalysts. Cellulose-SO3H still retained above 90% of its original catalytic activity even after 30 cycles of successive re-use, indicating excellent operational stability. It can be clearly seen that the Cellulose-SO3H catalyst displays tremendous potential for biodiesel production.

Key words: cellulose, solid acid catalyst, biodiesel, esterification, waste oil