酶法甘油解合成甘油二酯工艺的研究
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摘要
甘油二酯功能性食用油是以天然食用油为原料、通过生物酶法催化改性而成的新型油脂，具有明确的防止肥胖、降血脂等功能且食用安全，作为普通食用油的换代产品，能从根本上缓解我国居民高油脂、高热量的膳食结构所引起的肥胖、高血酯、糖尿病等慢性疾病日益流行的现状，在不改变现有饮食习惯的前提下调节人体亚健康水平及遏制相关慢性病的发生与发展。甘油二酯市场潜力近500亿元人民币，目前只有日本和美国可以生产，国内未见产业化报导。由于酯化工艺生产的甘油二酯产品中含有过量的缩水甘油酯，生产商已经于2009年停止生产，并召回了部分产品。
本课题在深入分析国内外研究现状的基础上，对甘油解反应进行了深入研究。首先考察了有机溶剂体系中甘油解反应制备甘油二酯的反应规律，发现叔丁醇为溶剂的甘油解反应中TAG转化率高(98.7%)，产物经分离后DAG纯度高(97.9%)，可用于实验室小规模地合成高纯度甘油二酯产品。有机溶剂体系不适用于工业化生产，本研究考察了固定化脂肪酶在无溶剂体系中催化甘油解反应合成甘油二酯的可行性。利用Lipozyme RMIM为催化剂时，在无溶剂体系中可以催化低甘油添加量（甘油与TAG摩尔比1:1）的甘油解反应合成DAG（甘油解产物中DAG含量55%以上），但酶的操作稳定性差，可有效重复使用的批次少；在反应体系中添加硅胶作为甘油的吸附载体可以提高酶的操作稳定性，有效增加Lipozyme RM IM的半衰期。填充床酶反应器，是固定化酶工业化应用的理想反应方式之一，本研究以填充床反应器的方式考察了三种商品化的固定化脂肪酶Lipozyme RM IM、Lipozyme TL IM、Novozym435催化无溶剂游离甘油体系甘油解反应合成甘油二酯的能力，发现Novozym435适用于甘油添加量较大（甘油与TAG的摩尔比2:1）的无溶剂游离甘油体系的甘油解反应（甘油解产物中DAG含量为55.02%），通过酶反应器的放大实验（20Kg）证明本工艺适于产业化应用。为了降低甘油解反应中催化剂的成本，将游离脂肪酶Lipozyme TL100L利用食品工业中常用的树脂吸附固定化，并将其用于填充床式反应器中催化甘油解反应合成甘油二酯，可以得到DAG含量为54.64%，MAG含量为17.47%，剩余的TAG为27.89%的甘油解产物。经分子蒸馏分离后，可以得到DAG含量为65.11%，TAG含量为34.89%的甘油二酯产品。将分子蒸馏后得到的甘油二酯产品进行脱色和脱臭处理，得到的甘油二酯产品具有良好的理化指标，缩水甘油酯的含量为0.747ppm，产品的稳定性与大豆色拉油相当。为了更有效地利用甘油解工艺过程中产生的MAG，利用新型偏甘油酯脂肪酶Lipase SMG1催化MAG与油酸反应合成了不含有TAG的甘油二酯产品。
本研究通过对甘油解反应的全面考察，建立了全酶法生产甘油二酯的新甘油解工艺，并结合分子蒸馏、油脂精炼等技术，建立了甘油解反应合成二酯的生产工艺，在实验室研究的基础上，成功的进行了甘油二酯酶法生产工艺的放大实验，形成了较为成熟的产业化工艺路线，能以较低的生产成本获得了纯度不低于60%的甘油二酯系列产品，产品符合国家的相关标准。该工艺具有反应效率较高、工艺操作简单、反应重现性好、生产成本低廉等优点，是制备中高含量的甘油二酯产品的适宜方法，达到了国内领先、国际先进的水平。
Diacylglycerol (DAG) functional edible oil is novel type of oil with unambiguousnutritional characteristics of the prevention of obesity and the decrease in postprandial serumtriacylglycerols (TAG), producted by enzymatic modification of natural edible oil.Diacylglycerol edible oil is safe in-use and can be used as upgrade and update products ofnormal edible oil, to radically relieve the actuality of increasingly prevalence rate of chronicdiseases of Chinese, such as obesity, hyperlipidemia, diabete, et al, caused by diet structurewith high oils and energy consumption, and to regulate human sub-health level and inhibitethe generating and developing of lifestyle-related chronic diseases with no change of existingdietetic habit. The potential maket value of diacylglycerol edible oil is about50000millionyuan. Now, diacylglycerol edible oil is producted only in Japan and American, and there is noreport on industrialization of diacylglycerol edible oil in China. In September2009Japonicfactories stopped diacylglycerol oil production because glycidol fatty acid esters at levels10to200times found in their products. Some non-Econa edible oil was recalled bymanufacturer.
Based on the in-depth analysis of the research status at inland and abroad, glycerolysisreaction was studied detailedly. Firstly, synthesis of diacylglycerol by lipase-catalysedglycerolysis was studied. Glycerolysis reaction in ter-betanol can be used to product highpurity diacylglycerol (97.9%) in laboratory scale because of the high conversion of TAG(98.7%). However, a glycerolysis reaction in an organic solvent also is unsuitable forindustrial production. The practicality of glycerolysis reaction in a solvent free system toproduct diacylglycerol oils was studied. Lipozyme RM IM can be used in glycerolysisreaction in a solvent free system to product diacylglycerol (DAG content was no less than55%) when the glycerol loadge was low (TAG/glycerol was1:1, mol/mol). Furthermore,Lipozyme RM IM was unstable because of free glycerol, glycerol must be adsorbed on silicagel before starting the reaction so as to achieve high yield and good operational stability,which is also unsuitable for large-scale industrial production. Three commercial immobilizedlipases, Lipozyme RM IM, Lipozyme TL IM and Novozym435, were screened for the production of DAGin a packed-bed reactor. Novozym435showed the best performance (DAG content was 55.02%in glycerides) and was selected to catalyze the glycerolysis reaction with abundantglycerol (glycerol/TAG2:1) in a solvent free system. It was proved that diacylglycerol oilscan be producted in this was after scale-up reaction (the mixture of substrate was20Kg) wasstudied in a packed-bed reactor. To reduce the production cost of DAG oil, Lipozyme TL100L was immobilized on resins and used to catalyzed glycerolysis reaction in a packed-bedreactor, mixture of glycerides with DAG54.64%, MAG17.47%, TAG27.89%was obtained.A diacyglycerol oil (DAG content was65.11%, TAG content was34.89%) was product afterpurification by molecular distillation. DAG oil with good physico-chemical properties wasobtained after decolor and deodorization, glycidol fatty acid esters content was0.747ppm.MAG producted in the glycerolysis reaction can be used to product DAG oil (with TAG)through esterification with oleic acid catalyzed by a novel partial glyceride lipase (LipaseSMG1).
A set of diacylglycerol oil production process was established by combination ofholoenzymatic process (glycerolysis reaction in a packed-bed reactor), molecular distillation,and oil refining technology. The successive scale-up of diacylglycerol production usingholoenzymatic process from laboratory-scale (gram scale) to pilot-scale (kilogram scale) wascarried out successfully, basing on the early research in lab. A diacylglycerol oil productionprocess that can be industrialized was devoleped, and no less than60%purity of theserialization diglyceride products, which measure up to national related standard and havequalification to sale promotion in the market, can be gained with the lower cost. Thisproduction process, which had the advantages of higher reaction efficiency, simpler processoperation, excellent repeatability of reaction, lower operating costs, et al, was a preferencemethod to synthesize a series of diacylglycerol product with more than60wt%diacylglycerolcontent and has reached the leading domestic and international advanced level.
本课题在深入分析国内外研究现状的基础上，对甘油解反应进行了深入研究。首先考察了有机溶剂体系中甘油解反应制备甘油二酯的反应规律，发现叔丁醇为溶剂的甘油解反应中TAG转化率高(98.7%)，产物经分离后DAG纯度高(97.9%)，可用于实验室小规模地合成高纯度甘油二酯产品。有机溶剂体系不适用于工业化生产，本研究考察了固定化脂肪酶在无溶剂体系中催化甘油解反应合成甘油二酯的可行性。利用Lipozyme RMIM为催化剂时，在无溶剂体系中可以催化低甘油添加量（甘油与TAG摩尔比1:1）的甘油解反应合成DAG（甘油解产物中DAG含量55%以上），但酶的操作稳定性差，可有效重复使用的批次少；在反应体系中添加硅胶作为甘油的吸附载体可以提高酶的操作稳定性，有效增加Lipozyme RM IM的半衰期。填充床酶反应器，是固定化酶工业化应用的理想反应方式之一，本研究以填充床反应器的方式考察了三种商品化的固定化脂肪酶Lipozyme RM IM、Lipozyme TL IM、Novozym435催化无溶剂游离甘油体系甘油解反应合成甘油二酯的能力，发现Novozym435适用于甘油添加量较大（甘油与TAG的摩尔比2:1）的无溶剂游离甘油体系的甘油解反应（甘油解产物中DAG含量为55.02%），通过酶反应器的放大实验（20Kg）证明本工艺适于产业化应用。为了降低甘油解反应中催化剂的成本，将游离脂肪酶Lipozyme TL100L利用食品工业中常用的树脂吸附固定化，并将其用于填充床式反应器中催化甘油解反应合成甘油二酯，可以得到DAG含量为54.64%，MAG含量为17.47%，剩余的TAG为27.89%的甘油解产物。经分子蒸馏分离后，可以得到DAG含量为65.11%，TAG含量为34.89%的甘油二酯产品。将分子蒸馏后得到的甘油二酯产品进行脱色和脱臭处理，得到的甘油二酯产品具有良好的理化指标，缩水甘油酯的含量为0.747ppm，产品的稳定性与大豆色拉油相当。为了更有效地利用甘油解工艺过程中产生的MAG，利用新型偏甘油酯脂肪酶Lipase SMG1催化MAG与油酸反应合成了不含有TAG的甘油二酯产品。
本研究通过对甘油解反应的全面考察，建立了全酶法生产甘油二酯的新甘油解工艺，并结合分子蒸馏、油脂精炼等技术，建立了甘油解反应合成二酯的生产工艺，在实验室研究的基础上，成功的进行了甘油二酯酶法生产工艺的放大实验，形成了较为成熟的产业化工艺路线，能以较低的生产成本获得了纯度不低于60%的甘油二酯系列产品，产品符合国家的相关标准。该工艺具有反应效率较高、工艺操作简单、反应重现性好、生产成本低廉等优点，是制备中高含量的甘油二酯产品的适宜方法，达到了国内领先、国际先进的水平。
Diacylglycerol (DAG) functional edible oil is novel type of oil with unambiguousnutritional characteristics of the prevention of obesity and the decrease in postprandial serumtriacylglycerols (TAG), producted by enzymatic modification of natural edible oil.Diacylglycerol edible oil is safe in-use and can be used as upgrade and update products ofnormal edible oil, to radically relieve the actuality of increasingly prevalence rate of chronicdiseases of Chinese, such as obesity, hyperlipidemia, diabete, et al, caused by diet structurewith high oils and energy consumption, and to regulate human sub-health level and inhibitethe generating and developing of lifestyle-related chronic diseases with no change of existingdietetic habit. The potential maket value of diacylglycerol edible oil is about50000millionyuan. Now, diacylglycerol edible oil is producted only in Japan and American, and there is noreport on industrialization of diacylglycerol edible oil in China. In September2009Japonicfactories stopped diacylglycerol oil production because glycidol fatty acid esters at levels10to200times found in their products. Some non-Econa edible oil was recalled bymanufacturer.
Based on the in-depth analysis of the research status at inland and abroad, glycerolysisreaction was studied detailedly. Firstly, synthesis of diacylglycerol by lipase-catalysedglycerolysis was studied. Glycerolysis reaction in ter-betanol can be used to product highpurity diacylglycerol (97.9%) in laboratory scale because of the high conversion of TAG(98.7%). However, a glycerolysis reaction in an organic solvent also is unsuitable forindustrial production. The practicality of glycerolysis reaction in a solvent free system toproduct diacylglycerol oils was studied. Lipozyme RM IM can be used in glycerolysisreaction in a solvent free system to product diacylglycerol (DAG content was no less than55%) when the glycerol loadge was low (TAG/glycerol was1:1, mol/mol). Furthermore,Lipozyme RM IM was unstable because of free glycerol, glycerol must be adsorbed on silicagel before starting the reaction so as to achieve high yield and good operational stability,which is also unsuitable for large-scale industrial production. Three commercial immobilizedlipases, Lipozyme RM IM, Lipozyme TL IM and Novozym435, were screened for the production of DAGin a packed-bed reactor. Novozym435showed the best performance (DAG content was 55.02%in glycerides) and was selected to catalyze the glycerolysis reaction with abundantglycerol (glycerol/TAG2:1) in a solvent free system. It was proved that diacylglycerol oilscan be producted in this was after scale-up reaction (the mixture of substrate was20Kg) wasstudied in a packed-bed reactor. To reduce the production cost of DAG oil, Lipozyme TL100L was immobilized on resins and used to catalyzed glycerolysis reaction in a packed-bedreactor, mixture of glycerides with DAG54.64%, MAG17.47%, TAG27.89%was obtained.A diacyglycerol oil (DAG content was65.11%, TAG content was34.89%) was product afterpurification by molecular distillation. DAG oil with good physico-chemical properties wasobtained after decolor and deodorization, glycidol fatty acid esters content was0.747ppm.MAG producted in the glycerolysis reaction can be used to product DAG oil (with TAG)through esterification with oleic acid catalyzed by a novel partial glyceride lipase (LipaseSMG1).
A set of diacylglycerol oil production process was established by combination ofholoenzymatic process (glycerolysis reaction in a packed-bed reactor), molecular distillation,and oil refining technology. The successive scale-up of diacylglycerol production usingholoenzymatic process from laboratory-scale (gram scale) to pilot-scale (kilogram scale) wascarried out successfully, basing on the early research in lab. A diacylglycerol oil productionprocess that can be industrialized was devoleped, and no less than60%purity of theserialization diglyceride products, which measure up to national related standard and havequalification to sale promotion in the market, can be gained with the lower cost. Thisproduction process, which had the advantages of higher reaction efficiency, simpler processoperation, excellent repeatability of reaction, lower operating costs, et al, was a preferencemethod to synthesize a series of diacylglycerol product with more than60wt%diacylglycerolcontent and has reached the leading domestic and international advanced level.
引文
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