固定化脂肪酶催化木本油脂制备生物柴油的研究
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摘要
来源于动植物油脂、废餐饮油脂的石化燃料替代产品—生物柴油具有可再生性、生物降解性及环境友好性等特点近来已引起了越来越多的关注。本文以香叶树、黄连木种子为实验原料,分析评价了油脂性质与脂肪酸组成,研究固定化脂肪酶催化香叶树籽油和黄连木籽油制备生物柴油技术,并对其生物柴油性能进行了评价。
油脂组成与性质研究表明,香叶树油脂脂肪酸组成以饱和短链脂肪酸为主,其中癸酸占33.48%、月桂酸占59.14%,香叶树籽油为低酸值油脂(酸值1.19mgKOH/g)皂化值为215.5mg KOH/g;黄连木籽油脂脂肪酸组成以不饱和长链脂肪酸为主,其中油酸46.77%、亚油酸34.43%,黄连木籽油为高酸值油脂(酸值18.03mgKOH/g),皂化值为155.3mgKOH/g。
建立反相高效液相色谱法(RP-HPLC)定量分析生物柴油中各组分,流动相为A相甲醇、B相异丙醇—正己烷(体积比5︰4混合),按0min 100%A,15min 50%A+50%B进行二元梯度洗脱,检测器波长210nm。建立了癸酸甲酯等六种脂肪酸甲酯标准品的标准曲线。间隔测定反应过程体系中组分的变化,用以快速监测油脂中甘油三酸酯转变为脂肪酸单酯的进程,并对脂肪酸单酯和甘油三酸酯进行定量监测。
应用响应面优化法法确定了固定化酶催化香叶树籽油反应制备生物柴油的最优工艺参数,采用叔丁醇作为反应体系的溶剂,Lipozyme TL IM脂肪酶作为催化剂,最佳反应条件为:反应温度38.5℃,甲醇与油摩尔比4∶1,叔丁醇与油体积比1∶1,酶用量为油重的4%,反应转化率达到90%。
进行了香叶树油脂生物柴油和黄连木油脂生物柴油密度、运动粘度、闪点、倾点、冷滤点、馏程、十六烷指数等性能指标评价,除香叶树生物柴油的闪点(115℃),黄连木生物柴油的运动粘度(6.42mm2/s)不符合美国(ASTM)标准外,其余指标均满足要求。
Biodiesel has appealing more people as an alternative to diesel fuels made from vegetable oils, animal fats or used frying oils. Biodiesel is renewable, biodegradable and environmentally benign. The materials used in this paper were Lindera Communis Hemsl(LCH) seed oil and Pistacia Chinensis Bunge (PCB) seed oil, the qualitative and quantitative composition of the oils and enzymatic ayntheses of biodiesel via LCH and PCB oils were studied. The performance of biodiesel had been evaluated.
The qualitative and quantitative composition of LCH and PCB: The acid value of LCH seed oil was 1.19mgKOH/g, saponification value 215.5mgKOH/g, the mainly composition of oil was saturated fatty acid(Capric acid 33.48%, Lauric acid 59.14%); The acid value of PCB seed oil was 18.03mgKOH/g, saponification value 155.3mgKOH/g, the mainly composition of oil was unsaturated fatty acid(Linoleic acid 34.43%, Octadecenoic acid 46.77%).
Study was carried out on gradient elution reversed-phase high-performance liquid chromatography (RP-HPLC), it was used for the determination of compounds occurring during the production of biodiesel from oil.Reservoir A contained methanol, reservoir B congtained 2-propanol-hexane (5:4,v/v). Builded six linear regression equations of fatty acid standards. A linear gradient from 100%A to 50%A +50%B in 15min. It was used for fast monitoring of conversion of the oil triacylglycerols to fatty acid methyl esters and for quantitation of residual TGs in the final biodiesel product.
The optimized parameters to catalyse LCH seed oil to biodiesel by the immobilized lipase were made by the Response Surface Methodology, tert-butanol was adopted as a reaction medium for lipase-catalyzed methanolysis of oils for biodiesel production, Lipozyme TLIM was used as catalyst, the biodiesel with best conversion 90% was produced at the reaction temperature, 38.5℃; the ratio of mole quantity between methanol and oil, 4; the ratio of volume between tert-butanol and oil, 1; Lipozyme TLIM catalyst concentration, 4%.
The biodiesel of LCH and PCB oil had the fuel properties such as density, kinematic viscosity, flash point, pour point, cold filter plugging point, cetane index, distillation temperature and fatty acid composition within the limits prescribed by the American (ASTM)standards, except for a slightly lower flash point(115℃)of LCH biodiesel and a higher kinematic viscosity(6.42mm2/s) of PCB biodiesel than that prescribed by the latter standard.
油脂组成与性质研究表明,香叶树油脂脂肪酸组成以饱和短链脂肪酸为主,其中癸酸占33.48%、月桂酸占59.14%,香叶树籽油为低酸值油脂(酸值1.19mgKOH/g)皂化值为215.5mg KOH/g;黄连木籽油脂脂肪酸组成以不饱和长链脂肪酸为主,其中油酸46.77%、亚油酸34.43%,黄连木籽油为高酸值油脂(酸值18.03mgKOH/g),皂化值为155.3mgKOH/g。
建立反相高效液相色谱法(RP-HPLC)定量分析生物柴油中各组分,流动相为A相甲醇、B相异丙醇—正己烷(体积比5︰4混合),按0min 100%A,15min 50%A+50%B进行二元梯度洗脱,检测器波长210nm。建立了癸酸甲酯等六种脂肪酸甲酯标准品的标准曲线。间隔测定反应过程体系中组分的变化,用以快速监测油脂中甘油三酸酯转变为脂肪酸单酯的进程,并对脂肪酸单酯和甘油三酸酯进行定量监测。
应用响应面优化法法确定了固定化酶催化香叶树籽油反应制备生物柴油的最优工艺参数,采用叔丁醇作为反应体系的溶剂,Lipozyme TL IM脂肪酶作为催化剂,最佳反应条件为:反应温度38.5℃,甲醇与油摩尔比4∶1,叔丁醇与油体积比1∶1,酶用量为油重的4%,反应转化率达到90%。
进行了香叶树油脂生物柴油和黄连木油脂生物柴油密度、运动粘度、闪点、倾点、冷滤点、馏程、十六烷指数等性能指标评价,除香叶树生物柴油的闪点(115℃),黄连木生物柴油的运动粘度(6.42mm2/s)不符合美国(ASTM)标准外,其余指标均满足要求。
Biodiesel has appealing more people as an alternative to diesel fuels made from vegetable oils, animal fats or used frying oils. Biodiesel is renewable, biodegradable and environmentally benign. The materials used in this paper were Lindera Communis Hemsl(LCH) seed oil and Pistacia Chinensis Bunge (PCB) seed oil, the qualitative and quantitative composition of the oils and enzymatic ayntheses of biodiesel via LCH and PCB oils were studied. The performance of biodiesel had been evaluated.
The qualitative and quantitative composition of LCH and PCB: The acid value of LCH seed oil was 1.19mgKOH/g, saponification value 215.5mgKOH/g, the mainly composition of oil was saturated fatty acid(Capric acid 33.48%, Lauric acid 59.14%); The acid value of PCB seed oil was 18.03mgKOH/g, saponification value 155.3mgKOH/g, the mainly composition of oil was unsaturated fatty acid(Linoleic acid 34.43%, Octadecenoic acid 46.77%).
Study was carried out on gradient elution reversed-phase high-performance liquid chromatography (RP-HPLC), it was used for the determination of compounds occurring during the production of biodiesel from oil.Reservoir A contained methanol, reservoir B congtained 2-propanol-hexane (5:4,v/v). Builded six linear regression equations of fatty acid standards. A linear gradient from 100%A to 50%A +50%B in 15min. It was used for fast monitoring of conversion of the oil triacylglycerols to fatty acid methyl esters and for quantitation of residual TGs in the final biodiesel product.
The optimized parameters to catalyse LCH seed oil to biodiesel by the immobilized lipase were made by the Response Surface Methodology, tert-butanol was adopted as a reaction medium for lipase-catalyzed methanolysis of oils for biodiesel production, Lipozyme TLIM was used as catalyst, the biodiesel with best conversion 90% was produced at the reaction temperature, 38.5℃; the ratio of mole quantity between methanol and oil, 4; the ratio of volume between tert-butanol and oil, 1; Lipozyme TLIM catalyst concentration, 4%.
The biodiesel of LCH and PCB oil had the fuel properties such as density, kinematic viscosity, flash point, pour point, cold filter plugging point, cetane index, distillation temperature and fatty acid composition within the limits prescribed by the American (ASTM)standards, except for a slightly lower flash point(115℃)of LCH biodiesel and a higher kinematic viscosity(6.42mm2/s) of PCB biodiesel than that prescribed by the latter standard.
引文
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