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Continuous enzymatic transesterification of high oleic sunflower oil in a packed bed reactor: influence of the glycerol production

机译:填充床反应器中高油酸葵花籽油的连续酶促酯交换反应:对甘油生产的影响

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The transesterification of high oleic sunflower oil with butanol by the immobilized Lipozyme in n-hexane was carried out in a continuous packed bed reactor, oleic acid, butyl ester, and glycerol being formed as the main products. It was found that glycerol, insoluble in n-hexane, remained in the reactor adsorbed onto the enzymatic support, leading to a drastic decrease in enzymatic activity. The phenomenon involved in this loss of activity was attributed to the formation of an hydrophilic hindrance around the enzyme resulting in diffusion limitations of the hydrophobic substrate from the organic phase to the enzyme. To recover enzymatic activity, several solutions are proposed. The addition of silica gel into the enzymatic bed to adsorb the produced glycerol did not enable this loss of activity to be avoided. In order to enhance the solubility of glycerol in the reaction medium as soon as it was produced, n-hexane amended acetone was used as solvent, but high conversion of sunflower oil was not restored. Finally, by intermittent rinsing of the catalyst bed with a solution of tertiary alcohol amended with water to obtain the optimal thermodynamic water activity of 0.54, glycerol was eliminated from the reactor, and high conversion was maintained. This semi-continuous process allowed not only the synthesis of oleic acid butyl ester but also the two products to be recovered separately.
机译:在固定床反应器中,通过固定化的Lipozyme在正己烷中进行的高油酸向日葵油与丁醇的酯交换反应,形成了油酸,丁酯和甘油为主要产物。发现不溶于正己烷的甘油保留在反应器中,吸附在酶载体上,导致酶活性急剧下降。这种活性丧失所涉及的现象归因于酶周围亲水性障碍的形成,导致疏水性底物从有机相向酶的扩散受限。为了恢复酶活性,提出了几种解决方案。将硅胶添加到酶床中以吸附产生的甘油不能避免这种活性损失。为了在产生甘油后立即增加其在反应介质中的溶解度,使用正己烷改性的丙酮作为溶剂,但是不能恢复向日葵油的高转化率。最后,通过用叔醇溶液加水修正间歇地漂洗催化剂床以获得最佳的0.54的热力学水活性,从反应器中除去了甘油,并保持了高转化率。该半连续过程不仅允许合成油酸丁酯,而且可以分别回收两种产物。

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