基于棉籽油和文冠果油催化合成生物柴油研究
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摘要
目前国际上石油和煤炭资源日益减少,严重制约着社会经济的发展,同时传统资源存在着严重的环保问题,因此新能源的研制开发是各国科研生产的战略重点。生物柴油因其原料可再生受到越来越多的关注,它具有含硫量极低、芳香烃含量少、含氧量高、十六烷值高、闪点高等优点。
采用GC-MS分别对棉籽油和文冠果种仁油的理化性能指标和脂肪酸组成进行了测定与分析,结果表明两种原料油主要由16-18碳链的脂肪酸组成,文冠果种仁油和棉籽油的化学组成均满足用作燃料替代品的条件。本体系以KOH为催化剂,分别以棉籽油和文冠果种仁油为原料采用正交实验方法对其工艺进行了优化,得出以棉籽油为原料的最佳反应条件为:醇油物质的量比6.5:1,催化剂用量1.1%,反应温度45℃,反应时间为40min,生物柴油的产率达到96.05%;以文冠果种仁油为原料的最佳反应条件为:醇油物质的量比6:1,催化剂用量0.8%,反应温度65℃,反应时间为75min,生物柴油的产率达到90.83%。
本文还针对油脂/甲醇不相溶特点将超声强化反应装置用于棉籽油/甲醇酯交换反应体系制备生物柴油。利用二次回归正交旋转组合设计超声强化棉籽油制备生物柴油实验,并用SAS软件对试验结果进行处理,得超声强化棉籽油制备生物柴油实验的数学模型为:
Y1 = 95.90667 + 0.015833X_1 + 0.660833X_2 + 2.228333X_3-0.045X_4- 0.709167X_1~2-0.5925X_1X_2 + 0.78X_1X_3-0.1X_1X_4-1.334167X_2~2-2.975X_2X_3-0.045X_2X_4-1.870417X_3~2 +0.085X_3X_4+0.709583X_4~2
最优工艺条件:超声时间(X_1)20 min,催化剂用量(X_2)0.9%,醇油比(X_3)6.5:1,,占空比(X_4)28%,得率(Y1)为97.35%。影响酯化率的因素顺序为:醇油比,催化剂用量,占空比,反应时间。
同时还研究了微波强化对棉籽油酯交换反应的工艺影响,分别从醇油比、催化剂用量、微波功率、强化时间四个水平来考察棉籽油的得率,用正交实验方法对其工艺进行了优化得出最佳反应条件为:醇油摩尔比9:1,催化剂用量1.0%,反应时间3 min,微波功率360W。
为了评价棉籽油和文冠果生物柴油是否可以作为普通柴油的替代燃料,研究了棉籽油生物柴油和文冠果生物柴油的组成和理化特性。结果表明棉籽油生物柴油和文冠果生物柴油闪点、硫含量、粘度、水分、酸值、密度、色度等指标基本达到国外EN14214生物柴油标准,与我国0#柴油的主要性能指标接近。
Petroleum and coal resources have been vanishing recently, which is seriously restricting socio-economic development and threatening the peace of the world. At the same time, serious environmental problems existed in traditional resources. So the research and development of new energy become a strategic focus of the researching production of all countries. Biodiesel is being paid more attention because of renewable materials. The characteristics of biodiesel owns some advantages, such as lack of sulfur and aroma hydrocarbon, rich of oxygen, high cetane value and high flash point, less hazardous exhaust gas. Synthesizing biodesel from cottonseed and Xanthoceras sorbifolia oil with KOH as catalysts was studied. At the same time, cottonseed biodiesel was prepared under ultrasonic wave and microwave.
It’s physical and chemical characteristics and fatty acid composition of cottonseed and Xanthoceras sorbifolia oil that become the key point of replacing resource for petroleum and coal resources. The results of GC-MS and other tests showed that the cottonseed and Xanthoceras sorbifolia oil mainly contented 16-18C. Cottonseed and Xanthoceras sorbifolia oil were ideal for alternative fuel subatitution due to molecular structure of its product was similar to disesl. Using cottonseed and Xanthoceras sorbifolia oil as raw material, KOH as catalyst, through orthogonal analysis, the optimum conditions of cottonseed oil as raw material were as follows: molar ratio of methanol to oil 6.5:1, catalyst dosage 1.1%, reaction temperature 45℃and reaction time 40 min and the conversion rate reached 96.05%. The optimum conditions of Xanthoceras sorbifolia oil as raw material were as follows: molar ratio of methanol to oil 6:1, catalyst dosage 0.8%, reaction temperature 65℃and reaction time 75 min and the conversion rate reached 90.83%.
Ultrasonic reaction equipment was designed and the effects of ultrasonic energy on the transesterification of cottonseed oil with methanol to biodiesel were investigated primarily. Results of quadratic regression orthogonal rotating design showed that the sequential factors affecting on degumming of cottonseed oil were molar ratio of methanol to oil, catalyst dosage, duty cycle and reaction time.The regression model obtained via SAS software for the degumming process was:
Y1 = 95.90667 + 0.015833X_1 + 0.660833X_2 + 2.228333X_3-0.045X_4- 0.709167X_1~2-0.5925X_1X_2 + 0.78X_1X_3-0.1X_1X_4-1.334167X_2~2-2.975X_2X_3-0.045X_2X_4-1.870417X_3~2 +0.085X_3X_4+0.709583X_4~2
The optimal conditions were molar ratio of methanol to cottonseed oil was 6.5:1, reaction time was 20min, duty cycle was 28% and catalyst dosage was 0.9%, the yields of biodiesel could reach 97.35%. Compared to the transesterification of mechanical stirring, the reaction time was shortened from 40min to 20min. It’s implied that emulsification and reaction enhancement of ultrasonic outfield cooperated well on improving the transesterification reaction.
The biodiesel was prepared by transesterification reaction assisted with microwave. The effect of the mole ratio of methanol to oil, catalyst dosage, reaction time and microwave power on transesterification were researched. Through orthogonal analysis, the optimum conditions were as follows: molar ratio of methanol to oil 9:1, catalyst dosage 1.0%, reaction time 3 min and microwave power 360 w. The conversion rate was more than 94.47% under the optimum conditions.
The physical and chemical characteristics of the biodiesel prepared by cottonseed and Xanthoceras sorbifolia oil were analyzed. The results met the quality criteria of the biodiesel produced from cottonseed oil and Xanthoceras sorbifolia oil meet the same standards 0#diesel and EN14214 of Europe.
采用GC-MS分别对棉籽油和文冠果种仁油的理化性能指标和脂肪酸组成进行了测定与分析,结果表明两种原料油主要由16-18碳链的脂肪酸组成,文冠果种仁油和棉籽油的化学组成均满足用作燃料替代品的条件。本体系以KOH为催化剂,分别以棉籽油和文冠果种仁油为原料采用正交实验方法对其工艺进行了优化,得出以棉籽油为原料的最佳反应条件为:醇油物质的量比6.5:1,催化剂用量1.1%,反应温度45℃,反应时间为40min,生物柴油的产率达到96.05%;以文冠果种仁油为原料的最佳反应条件为:醇油物质的量比6:1,催化剂用量0.8%,反应温度65℃,反应时间为75min,生物柴油的产率达到90.83%。
本文还针对油脂/甲醇不相溶特点将超声强化反应装置用于棉籽油/甲醇酯交换反应体系制备生物柴油。利用二次回归正交旋转组合设计超声强化棉籽油制备生物柴油实验,并用SAS软件对试验结果进行处理,得超声强化棉籽油制备生物柴油实验的数学模型为:
Y1 = 95.90667 + 0.015833X_1 + 0.660833X_2 + 2.228333X_3-0.045X_4- 0.709167X_1~2-0.5925X_1X_2 + 0.78X_1X_3-0.1X_1X_4-1.334167X_2~2-2.975X_2X_3-0.045X_2X_4-1.870417X_3~2 +0.085X_3X_4+0.709583X_4~2
最优工艺条件:超声时间(X_1)20 min,催化剂用量(X_2)0.9%,醇油比(X_3)6.5:1,,占空比(X_4)28%,得率(Y1)为97.35%。影响酯化率的因素顺序为:醇油比,催化剂用量,占空比,反应时间。
同时还研究了微波强化对棉籽油酯交换反应的工艺影响,分别从醇油比、催化剂用量、微波功率、强化时间四个水平来考察棉籽油的得率,用正交实验方法对其工艺进行了优化得出最佳反应条件为:醇油摩尔比9:1,催化剂用量1.0%,反应时间3 min,微波功率360W。
为了评价棉籽油和文冠果生物柴油是否可以作为普通柴油的替代燃料,研究了棉籽油生物柴油和文冠果生物柴油的组成和理化特性。结果表明棉籽油生物柴油和文冠果生物柴油闪点、硫含量、粘度、水分、酸值、密度、色度等指标基本达到国外EN14214生物柴油标准,与我国0#柴油的主要性能指标接近。
Petroleum and coal resources have been vanishing recently, which is seriously restricting socio-economic development and threatening the peace of the world. At the same time, serious environmental problems existed in traditional resources. So the research and development of new energy become a strategic focus of the researching production of all countries. Biodiesel is being paid more attention because of renewable materials. The characteristics of biodiesel owns some advantages, such as lack of sulfur and aroma hydrocarbon, rich of oxygen, high cetane value and high flash point, less hazardous exhaust gas. Synthesizing biodesel from cottonseed and Xanthoceras sorbifolia oil with KOH as catalysts was studied. At the same time, cottonseed biodiesel was prepared under ultrasonic wave and microwave.
It’s physical and chemical characteristics and fatty acid composition of cottonseed and Xanthoceras sorbifolia oil that become the key point of replacing resource for petroleum and coal resources. The results of GC-MS and other tests showed that the cottonseed and Xanthoceras sorbifolia oil mainly contented 16-18C. Cottonseed and Xanthoceras sorbifolia oil were ideal for alternative fuel subatitution due to molecular structure of its product was similar to disesl. Using cottonseed and Xanthoceras sorbifolia oil as raw material, KOH as catalyst, through orthogonal analysis, the optimum conditions of cottonseed oil as raw material were as follows: molar ratio of methanol to oil 6.5:1, catalyst dosage 1.1%, reaction temperature 45℃and reaction time 40 min and the conversion rate reached 96.05%. The optimum conditions of Xanthoceras sorbifolia oil as raw material were as follows: molar ratio of methanol to oil 6:1, catalyst dosage 0.8%, reaction temperature 65℃and reaction time 75 min and the conversion rate reached 90.83%.
Ultrasonic reaction equipment was designed and the effects of ultrasonic energy on the transesterification of cottonseed oil with methanol to biodiesel were investigated primarily. Results of quadratic regression orthogonal rotating design showed that the sequential factors affecting on degumming of cottonseed oil were molar ratio of methanol to oil, catalyst dosage, duty cycle and reaction time.The regression model obtained via SAS software for the degumming process was:
Y1 = 95.90667 + 0.015833X_1 + 0.660833X_2 + 2.228333X_3-0.045X_4- 0.709167X_1~2-0.5925X_1X_2 + 0.78X_1X_3-0.1X_1X_4-1.334167X_2~2-2.975X_2X_3-0.045X_2X_4-1.870417X_3~2 +0.085X_3X_4+0.709583X_4~2
The optimal conditions were molar ratio of methanol to cottonseed oil was 6.5:1, reaction time was 20min, duty cycle was 28% and catalyst dosage was 0.9%, the yields of biodiesel could reach 97.35%. Compared to the transesterification of mechanical stirring, the reaction time was shortened from 40min to 20min. It’s implied that emulsification and reaction enhancement of ultrasonic outfield cooperated well on improving the transesterification reaction.
The biodiesel was prepared by transesterification reaction assisted with microwave. The effect of the mole ratio of methanol to oil, catalyst dosage, reaction time and microwave power on transesterification were researched. Through orthogonal analysis, the optimum conditions were as follows: molar ratio of methanol to oil 9:1, catalyst dosage 1.0%, reaction time 3 min and microwave power 360 w. The conversion rate was more than 94.47% under the optimum conditions.
The physical and chemical characteristics of the biodiesel prepared by cottonseed and Xanthoceras sorbifolia oil were analyzed. The results met the quality criteria of the biodiesel produced from cottonseed oil and Xanthoceras sorbifolia oil meet the same standards 0#diesel and EN14214 of Europe.
引文
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