离子液体催化制备生物柴油的比较研究
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摘要
目的：以棉籽油为原料,进行离子液体、氢氧化钠和脂肪酶作为催化剂制备生物柴油的工艺比较研究,以脂肪酸甲酯的收率为指标,考察了影响酯交换反应的因素,通过正交实验得到离子液体催化酯交换反应的优化工艺条件。
方法：分别使用离子液体、氢氧化钠和脂肪酶作为催化剂催化棉籽油制备生物柴油。利用薄层层析色谱和高效液相色谱对生物柴油进行定性、定量分析,并获得其收率。通过单因素多水平实验及正交实验优化酯交换反应的工艺条件,比较分析各种催化剂的催化效果、稳定性、经济性及环境友好性。
结果：
1.棉籽油在离子液体[Bmim]OH催化下,酯交换反应制取生物柴油的影响因素依次为：醇油摩尔比>催化剂用量>反应时间>反应温度；[Bmim]OH催化制备生物柴油的优化条件是醇油摩尔比7：1,催化剂用量3.5%,反应时间50min；反应温度55℃；在该条件下脂肪酸甲酯的收率在91.7%-93.5%之间,离子液体[Bmim]OH性质稳定,能重复使用6次以上。
2.棉籽油在离子液体[Emim]OH催化下,酯交换反应制取生物柴油的影响因素依次为：醇油摩尔比>反应温度>反应时间>催化剂用量；[Emim]OH催化制备生物柴油的优化条件是醇油摩尔比6：1,催化剂用量3.5%,反应时间50min；反应温度55℃；在该条件下脂肪酸甲酯的收率在89.8%-90.7%之间；离子液体[Emim]OH性质稳定,能重复使用6次以上。
3.棉籽油在NaOH催化下,酯交换反应制取生物柴油的影响因素依次为：醇油摩尔比>反应时间>催化剂用量>反应温度；NaOH催化制备生物柴油的优化条件是醇油摩尔比7：1,催化剂用量1.4%,反应时间60min,反应温度55℃;在该条件下脂肪酸甲酯的收率在89.7%-90.9%之间。
4.棉籽油在生物酶Nov435催化下,酯交换反应制备生物柴油的工艺条件是：醇油摩尔比为3.5：1、酶用量为10%、反应温度为50℃、转速为160r/min,反应时间24h,在此条件下进行酶催化制备生物柴油的验证实验,实验表明脂肪酸甲酯收率均在90%以上,而且酶催化剂处理后能重复利用。
结论：
1.利用离子液体、氢氧化钠和生物酶催化制备了棉籽油生物柴油,利用高效液相色谱和薄层层析色谱定性、定量分析了产物。
2.运用单因素多水平实验及正交实验分析醇油摩尔比、催化剂用量、反应时间等因素对酯交换反应的影响,并获得四种催化剂催化制备棉籽油生物柴油的优化反应条件。
3.通过对催化剂催化性能、稳定性、经济性及环境友好性的比较,表明离子液体是生物柴油制备工艺中较优越的催化剂。
Object:Comparative research on transesterification of cottonseed oil used ionic liquids ([BmimJOH, [Emim]OH), NaOH and Nov435 as catalysts. The effect of the molar ratio of methanol to oil, amount of the catalyst, reaction time and temperature on transesterification by the yield of biodiesel were obtained, and the optimum conditions was acknowledged by [Bmim]OH as catalysts through orthogonal analysis.
Methods:Prepared cottonseed oil biodiesel by ionic liquids ([Bmim]OH, [Emim]OH), NaOH and Nov435 as catalysts. Qualitative and quantitative analysis of biodiesel were followed by HPLC chromatography and Thin-layer chromatography. And the single-factor's effect and the optimized reaction conditions were obtained through multi-level and single-factor experiments and orthogonal experiments. The yield of biodiesel, the stability, the repeatedly use and cost by different catalysts was comparatively analyzed.
Results:
1. Produced cottonseed oil biodiesel by [Bmim]OH as catalyst. Determined the four important factors by the orthogonal experiments, and the results are as follows:molar ratio of methanol to oil>amount of the catalyst>time of reaction>temperature of reaction and the optimum condition is that molar ratio of methanol to oil is 7:1, amount of catalyst is 3.5%, time of reaction is 50min and temperature of reaction is 55℃, the yield of biodiesel from 91.7% to 93.5%; and the catalyst is steady and can be used repeatedly more than 6 times.
2. Produced cottonseed oil biodiesel by [Emim]OH as catalyst. Determined the four important factors by the orthogonal experiments, and the results are as follows:molar ratio of methanol to oil>temperature of reaction>time of reaction> amount of the catalyst and the optimum condition is that molar ratio of methanol to oil is 6:1, amount of catalyst is 3.5%, time of reaction is 50min and temperature of reaction is 55℃, the yield of biodiesel from 89.8% to 90.7%; and the catalyst is steady and can be used repeatedly more than 6 times.
3. Produced cottonseed oil biodiesel by NaOH as catalyst. Determined the four important factors by the orthogonal experiments, and the results are as follows:molar ratio of methanol to oil>time of reaction >amount of the catalyst>temperature of reaction and the optimum condition is that molar ratio of methanol to oil is 7:1, amount of catalyst is 1.4%, time of reaction is 60min and temperature of reaction is 55℃, the yield of biodiesel from 89.7% to 90.9%.
4. Produced cottonseed oil biodiesel by Nov435 as catalyst. Obtained the reaction conditions which are the molar ratio of methanol to oil is 3.5:1, amount of catalyst is 10%, time of reaction is 24h, temperature of reaction is 50℃and the stirring speed is 160r/min. Yield of biodiesel is all above 90%, and the catalyst can be used repeatedly after processed by organic solvents.
Conclusion:
1. Prepared cottonseed oil biodiesel by ionic liquids, NaOH and Nov435 as catalysts. Qualitative and quantitative analysis of biodiesel were followed by HPLC chromatography and Thin-layer chromatography.
2. Weighed the importance of different factors which are the molar ratio of methanol to oil, amount of the catalyst, time of reaction and temperature of reaction, and obtained the optimized reaction conditions through multi-level and single-factor experiments and orthogonal experiments.
3. Compared the yield of biodiesel under the optimum conditions, and analyzed the cost, the time of the repeatedly use and the environmental effect of the four catalysts, and [Bmim]OH was acknowledged as the superior catalyst, and it will be widely used in the future.
方法：分别使用离子液体、氢氧化钠和脂肪酶作为催化剂催化棉籽油制备生物柴油。利用薄层层析色谱和高效液相色谱对生物柴油进行定性、定量分析,并获得其收率。通过单因素多水平实验及正交实验优化酯交换反应的工艺条件,比较分析各种催化剂的催化效果、稳定性、经济性及环境友好性。
结果：
1.棉籽油在离子液体[Bmim]OH催化下,酯交换反应制取生物柴油的影响因素依次为：醇油摩尔比>催化剂用量>反应时间>反应温度；[Bmim]OH催化制备生物柴油的优化条件是醇油摩尔比7：1,催化剂用量3.5%,反应时间50min；反应温度55℃；在该条件下脂肪酸甲酯的收率在91.7%-93.5%之间,离子液体[Bmim]OH性质稳定,能重复使用6次以上。
2.棉籽油在离子液体[Emim]OH催化下,酯交换反应制取生物柴油的影响因素依次为：醇油摩尔比>反应温度>反应时间>催化剂用量；[Emim]OH催化制备生物柴油的优化条件是醇油摩尔比6：1,催化剂用量3.5%,反应时间50min；反应温度55℃；在该条件下脂肪酸甲酯的收率在89.8%-90.7%之间；离子液体[Emim]OH性质稳定,能重复使用6次以上。
3.棉籽油在NaOH催化下,酯交换反应制取生物柴油的影响因素依次为：醇油摩尔比>反应时间>催化剂用量>反应温度；NaOH催化制备生物柴油的优化条件是醇油摩尔比7：1,催化剂用量1.4%,反应时间60min,反应温度55℃;在该条件下脂肪酸甲酯的收率在89.7%-90.9%之间。
4.棉籽油在生物酶Nov435催化下,酯交换反应制备生物柴油的工艺条件是：醇油摩尔比为3.5：1、酶用量为10%、反应温度为50℃、转速为160r/min,反应时间24h,在此条件下进行酶催化制备生物柴油的验证实验,实验表明脂肪酸甲酯收率均在90%以上,而且酶催化剂处理后能重复利用。
结论：
1.利用离子液体、氢氧化钠和生物酶催化制备了棉籽油生物柴油,利用高效液相色谱和薄层层析色谱定性、定量分析了产物。
2.运用单因素多水平实验及正交实验分析醇油摩尔比、催化剂用量、反应时间等因素对酯交换反应的影响,并获得四种催化剂催化制备棉籽油生物柴油的优化反应条件。
3.通过对催化剂催化性能、稳定性、经济性及环境友好性的比较,表明离子液体是生物柴油制备工艺中较优越的催化剂。
Object:Comparative research on transesterification of cottonseed oil used ionic liquids ([BmimJOH, [Emim]OH), NaOH and Nov435 as catalysts. The effect of the molar ratio of methanol to oil, amount of the catalyst, reaction time and temperature on transesterification by the yield of biodiesel were obtained, and the optimum conditions was acknowledged by [Bmim]OH as catalysts through orthogonal analysis.
Methods:Prepared cottonseed oil biodiesel by ionic liquids ([Bmim]OH, [Emim]OH), NaOH and Nov435 as catalysts. Qualitative and quantitative analysis of biodiesel were followed by HPLC chromatography and Thin-layer chromatography. And the single-factor's effect and the optimized reaction conditions were obtained through multi-level and single-factor experiments and orthogonal experiments. The yield of biodiesel, the stability, the repeatedly use and cost by different catalysts was comparatively analyzed.
Results:
1. Produced cottonseed oil biodiesel by [Bmim]OH as catalyst. Determined the four important factors by the orthogonal experiments, and the results are as follows:molar ratio of methanol to oil>amount of the catalyst>time of reaction>temperature of reaction and the optimum condition is that molar ratio of methanol to oil is 7:1, amount of catalyst is 3.5%, time of reaction is 50min and temperature of reaction is 55℃, the yield of biodiesel from 91.7% to 93.5%; and the catalyst is steady and can be used repeatedly more than 6 times.
2. Produced cottonseed oil biodiesel by [Emim]OH as catalyst. Determined the four important factors by the orthogonal experiments, and the results are as follows:molar ratio of methanol to oil>temperature of reaction>time of reaction> amount of the catalyst and the optimum condition is that molar ratio of methanol to oil is 6:1, amount of catalyst is 3.5%, time of reaction is 50min and temperature of reaction is 55℃, the yield of biodiesel from 89.8% to 90.7%; and the catalyst is steady and can be used repeatedly more than 6 times.
3. Produced cottonseed oil biodiesel by NaOH as catalyst. Determined the four important factors by the orthogonal experiments, and the results are as follows:molar ratio of methanol to oil>time of reaction >amount of the catalyst>temperature of reaction and the optimum condition is that molar ratio of methanol to oil is 7:1, amount of catalyst is 1.4%, time of reaction is 60min and temperature of reaction is 55℃, the yield of biodiesel from 89.7% to 90.9%.
4. Produced cottonseed oil biodiesel by Nov435 as catalyst. Obtained the reaction conditions which are the molar ratio of methanol to oil is 3.5:1, amount of catalyst is 10%, time of reaction is 24h, temperature of reaction is 50℃and the stirring speed is 160r/min. Yield of biodiesel is all above 90%, and the catalyst can be used repeatedly after processed by organic solvents.
Conclusion:
1. Prepared cottonseed oil biodiesel by ionic liquids, NaOH and Nov435 as catalysts. Qualitative and quantitative analysis of biodiesel were followed by HPLC chromatography and Thin-layer chromatography.
2. Weighed the importance of different factors which are the molar ratio of methanol to oil, amount of the catalyst, time of reaction and temperature of reaction, and obtained the optimized reaction conditions through multi-level and single-factor experiments and orthogonal experiments.
3. Compared the yield of biodiesel under the optimum conditions, and analyzed the cost, the time of the repeatedly use and the environmental effect of the four catalysts, and [Bmim]OH was acknowledged as the superior catalyst, and it will be widely used in the future.
引文
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