绿色工艺制备生物柴油探索
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摘要
本文通过对食用油脂高温煎炸质量发生劣变及各种品质因子相关性研究，了解油脂劣变的基础上，以收集到的废油脂为原料，开展了原料预处理、碱性脂肪酶筛选、酶固定化工艺及参数、固定化酶性质、废油脂生物柴油传统催化制备工艺和固定化酶催化工艺比较，以及制备的生物柴油性能指标检测等研究工作，形成了新的脂肪酶固定化方法，酶法制备的生物柴油可以满足使用要求。
本文的主要结论是：
1．大豆油在180℃高温煎炸质13h左右，其理化指标即超过国家煎炸油标准，应当作废油脂处理，而废油脂的主要成分仍然是脂肪酸。
2．采用酯化-酯交换两步法转化高酸值废油脂，确定了酯化预处理降酸值的最优工艺条件，废油脂的酸值可从117.21mgKOH／g降至小于2mgKOH／g的水平。
3．以魔芋葡甘聚糖为载体，采用包埋法，进行脂肪酶的膜固定化研究，确定了酶固定化的最优工艺条件为：0.6％KGM的乳化剂SP-60，用Ca(OH)2调节pH值至11.0，酶液用量．03ml／gKGM，在低温通风干燥，所得固定化脂肪酶的活力为51.26U／g；对所固定酶的性质研究表明，最适反应温度35℃-55℃，最适pH值5.5和7.7；扫描电镜结果显示，包埋材料结构比较致密。
4．用二次回归旋转正交试验设计和响应面法确定了固定化酶催化废油脂反应制备生物柴油的最优工艺参数，即反应温度40.89℃-43.26℃，反应时间13.08h-13.79h，醇油物质量比2.71-2.25，加水量7.74％-9.68％，分三次加入甲醇。
5．酶法和化学法制得的生物柴油样品质量指标基本上符合现行美国和欧盟生物柴油标准，废油脂经酶法制备生物柴油是可行的。
In this paper, the quality inferior process of cooking oil in high temperature and the relationship among the quality factors were investigated. Based on the former work and the collection of wasted, the researches processed included the pretreatment of raw wasted oil, the screening of based lipases, the immobilization procedure of the enzyme and its property, the technology comparison of normal catalysis with the immobilized enzymatic catalysis, and the tests of performance index of biodiesel prepared by the two methods. The new carrier for the enzyme was selected, and so did the immobilization method. The quality of biodiesel made by the enzymatic technique can satisfy the utilization requirement.
The main conclusions were:
1. The refined soybean oil could be treated as wasted oil cooking around 13h at 180℃, because its chemical-physical index are beyond the limits of State cooking oil standard. But its main components were still fat acids.
2. The process of two-step, that is esterification and ester exchange was used to transform the high free acid oil to biodiesel. The optimized parameters to lower the acid value were obtained, and the acid value of the wasted oil could be reduced from the level of 117.21mgKOH/g to 2mgKOH/g.
3. The process of membrane immobilization of lipase was studied using the konjac glucamannon as carrier by the method of package. And the optimized parameters were: the emusifier of SP-60 with the quantity of 0.6% of KGM used, the pH value adjusted to 11.0 by Ca(OH)2 liquid, the enzyme liquid with the quantity of 0.03ml/gKGM also used. The immobilized enzyme was air-dryed under low temperature, and its activity was 51.26U/g. The property of the immobilized enzyme was also studied as the optimized temperature 35℃-55℃, pH value 5.5 and 7.7 separately. The result observed by SEM showed that the package frame was dense and close.
4. The optimized parameters to catalyse wasted cooking oil to biodiesel by the immobilized enzyme were made by the Quadratic Orthogonal Rorarional Regression Design and Response Surface Methodology, the reaction temperature 40.89℃-43.26℃, reaction time 13.08 h-13.79h, the ratio of quantity between methanol and oil 2.71-2.25, the amount of water 7.74%-9.68% added, the methanol added thrice.
5. Basically, performance index of the biodiesel made by both enzymatic and chemical methods were in accordance with the standards of biodiesel executed nowadays in USA and EU. And the procedure to produce biodiesel by enzyme technique is feasible.
本文的主要结论是：
1．大豆油在180℃高温煎炸质13h左右，其理化指标即超过国家煎炸油标准，应当作废油脂处理，而废油脂的主要成分仍然是脂肪酸。
2．采用酯化-酯交换两步法转化高酸值废油脂，确定了酯化预处理降酸值的最优工艺条件，废油脂的酸值可从117.21mgKOH／g降至小于2mgKOH／g的水平。
3．以魔芋葡甘聚糖为载体，采用包埋法，进行脂肪酶的膜固定化研究，确定了酶固定化的最优工艺条件为：0.6％KGM的乳化剂SP-60，用Ca(OH)2调节pH值至11.0，酶液用量．03ml／gKGM，在低温通风干燥，所得固定化脂肪酶的活力为51.26U／g；对所固定酶的性质研究表明，最适反应温度35℃-55℃，最适pH值5.5和7.7；扫描电镜结果显示，包埋材料结构比较致密。
4．用二次回归旋转正交试验设计和响应面法确定了固定化酶催化废油脂反应制备生物柴油的最优工艺参数，即反应温度40.89℃-43.26℃，反应时间13.08h-13.79h，醇油物质量比2.71-2.25，加水量7.74％-9.68％，分三次加入甲醇。
5．酶法和化学法制得的生物柴油样品质量指标基本上符合现行美国和欧盟生物柴油标准，废油脂经酶法制备生物柴油是可行的。
In this paper, the quality inferior process of cooking oil in high temperature and the relationship among the quality factors were investigated. Based on the former work and the collection of wasted, the researches processed included the pretreatment of raw wasted oil, the screening of based lipases, the immobilization procedure of the enzyme and its property, the technology comparison of normal catalysis with the immobilized enzymatic catalysis, and the tests of performance index of biodiesel prepared by the two methods. The new carrier for the enzyme was selected, and so did the immobilization method. The quality of biodiesel made by the enzymatic technique can satisfy the utilization requirement.
The main conclusions were:
1. The refined soybean oil could be treated as wasted oil cooking around 13h at 180℃, because its chemical-physical index are beyond the limits of State cooking oil standard. But its main components were still fat acids.
2. The process of two-step, that is esterification and ester exchange was used to transform the high free acid oil to biodiesel. The optimized parameters to lower the acid value were obtained, and the acid value of the wasted oil could be reduced from the level of 117.21mgKOH/g to 2mgKOH/g.
3. The process of membrane immobilization of lipase was studied using the konjac glucamannon as carrier by the method of package. And the optimized parameters were: the emusifier of SP-60 with the quantity of 0.6% of KGM used, the pH value adjusted to 11.0 by Ca(OH)2 liquid, the enzyme liquid with the quantity of 0.03ml/gKGM also used. The immobilized enzyme was air-dryed under low temperature, and its activity was 51.26U/g. The property of the immobilized enzyme was also studied as the optimized temperature 35℃-55℃, pH value 5.5 and 7.7 separately. The result observed by SEM showed that the package frame was dense and close.
4. The optimized parameters to catalyse wasted cooking oil to biodiesel by the immobilized enzyme were made by the Quadratic Orthogonal Rorarional Regression Design and Response Surface Methodology, the reaction temperature 40.89℃-43.26℃, reaction time 13.08 h-13.79h, the ratio of quantity between methanol and oil 2.71-2.25, the amount of water 7.74%-9.68% added, the methanol added thrice.
5. Basically, performance index of the biodiesel made by both enzymatic and chemical methods were in accordance with the standards of biodiesel executed nowadays in USA and EU. And the procedure to produce biodiesel by enzyme technique is feasible.
引文
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