CN1699516A - Process for preparing bio-diesel-oil by using microalgae fat - Google Patents
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Abstract
本发明公开了属于生物工程与能源领域的一种利用微藻油脂制备生物柴油的方法。在微藻油脂中加入一定量的甲醇,加热至一定的温度,在酸催化剂作用下,反应生成生物柴油。微藻生物柴油的密度为0.864kgl-1、粘度5.2×10-4 (40℃)、热值高达41MJ kg-1,这些特征与传统柴油相当。该技术为最终用生物和工程技术生产可再生能源并解决环境污染问题提供基础和科学依据,并具良好的应用和市场需求。
The invention discloses a method for preparing biodiesel from microalgae oil, which belongs to the field of bioengineering and energy. A certain amount of methanol is added to microalgae oil, heated to a certain temperature, and reacted to generate biodiesel under the action of an acid catalyst. The density of microalgae biodiesel is 0.864kgl -1 , the viscosity is 5.2×10 -4 (40℃), and the calorific value is as high as 41MJ kg -1 , which are comparable to traditional diesel oil. This technology provides a basic and scientific basis for the final use of biological and engineering technology to produce renewable energy and solve environmental pollution problems, and has good application and market demand.
Description
技术领域technical field
本发明属于生物工程与能源领域,涉及一种利用微藻油脂制备生物柴油的方法。The invention belongs to the field of bioengineering and energy, and relates to a method for preparing biodiesel from microalgae oil.
背景技术Background technique
生物柴油即脂肪酸甲酯,是一种可生物降解、无毒的可再生能源。由于石油资源的枯竭以及环保法规加强,世界各国积极开展对生物柴油的研制和生产。自1988年以来,许多欧洲国家就已经开始将生物柴油作为传统柴油的替代品加以利用了。但是由于较高的原材料成本,使得生物柴油的价格高于传统柴油。因此选取合适的、低成本的植物油脂资源来积极发展和生产生物柴油是发展的总趋势。Biodiesel, or fatty acid methyl ester, is a biodegradable, non-toxic renewable energy source. Due to the depletion of oil resources and the strengthening of environmental regulations, countries around the world are actively developing and producing biodiesel. Since 1988, many European countries have used biodiesel as an alternative to conventional diesel. However, due to the higher cost of raw materials, the price of biodiesel is higher than that of traditional diesel. Therefore, it is a general trend to choose suitable and low-cost vegetable oil resources to actively develop and produce biodiesel.
藻类具有光合作用效率高、环境适应能力强、生长周期短、生物产量高的特点,因此藻类是制备生物油燃料的良好材料。异养生长不仅可以提高生长效率,还有利于藻细胞内某些代谢产物如脂类等的积累,获得高脂肪含量的微藻,从而可降低生物质生产和油脂生产的成本。然而目前有关生物柴油制备的研究基本上都集中于蔬菜油如大豆油、葵花子油以及油菜籽等方面,未见异养微藻油脂制备生物柴油的报导。生产生物柴油最常用的方法是酯交换法,即在植物油中加入一定量的甲醇,加热至一定的温度,在催化剂(酸,碱或酶)作用下,反应生成脂肪酸甲酯,并分离出副产品甘油的过程。将这种酯交换反应技术与异养转化细胞工程技术整合,我们提出了一种利用异养藻油脂制备高质量生物柴油的方法。研究结果表明,利用异养藻油脂通过酸催化的酯交换反应可获得与传统柴油相当的生物柴油,其应用价值更高。Algae have the characteristics of high photosynthetic efficiency, strong environmental adaptability, short growth cycle, and high biological yield, so algae are good materials for preparing bio-oil fuels. Heterotrophic growth can not only improve growth efficiency, but also facilitate the accumulation of certain metabolites such as lipids in algal cells, and obtain microalgae with high fat content, thereby reducing the cost of biomass production and oil production. However, the current research on biodiesel production basically focuses on vegetable oils such as soybean oil, sunflower oil, and rapeseed, and there is no report on the preparation of biodiesel from heterotrophic microalgae oil. The most commonly used method for producing biodiesel is transesterification, that is, adding a certain amount of methanol to vegetable oil, heating it to a certain temperature, and reacting with a catalyst (acid, alkali or enzyme) to generate fatty acid methyl ester, and separating out by-products Glycerin process. Integrating this transesterification reaction technology with heterotrophic transformation cell engineering technology, we proposed a method to produce high-quality biodiesel from heterotrophic algae oil. The research results show that the biodiesel equivalent to traditional diesel can be obtained through acid-catalyzed transesterification by using heterotrophic algae oil, and its application value is higher.
发明内容Contents of the invention
本发明的目的是提供一种利用微藻油脂制备生物柴油的方法,其特征在于:所述的生物柴油是利用微藻油脂通过酯交换法获得的;其制备过程为:The object of the present invention is to provide a kind of method utilizing microalgae oil to prepare biodiesel, it is characterized in that: described biodiesel utilizes microalgae oil to obtain by transesterification; Its preparation process is:
(1)收集微藻,然后干燥并制成藻粉;(1) collect microalgae, then dry and make algae powder;
(2)利用植物油法从藻粉中提取微藻油脂;(2) Utilize vegetable oil method to extract microalgae oil from algae flour;
(3)酯交换反应:微藻油脂中加入醇油摩尔比为25∶1~84∶1的甲醇,加热至30℃~90℃,在浓硫酸催化作用下,反应生成脂肪酸甲酯即生物柴油,并分离出副产品甘油。(3) Transesterification reaction: add methanol with an alcohol-to-oil molar ratio of 25:1 to 84:1 to the microalgae oil, heat it to 30°C to 90°C, and react under the catalysis of concentrated sulfuric acid to generate fatty acid methyl ester, which is biodiesel , and the by-product glycerol is separated.
本发明的有益效果是1.利用微藻油脂经酯交换反应可获得高质量的生物柴油,其特性与传统的化石柴油相当。2.具有良好的应用和市场需求。The beneficial effects of the present invention are: 1. High-quality biodiesel can be obtained through transesterification by utilizing microalgae oil, and its characteristics are equivalent to those of traditional fossil diesel. 2. It has good application and market demand.
附图说明Description of drawings
图1(a)(b)为不同温度和催化剂条件下生物柴油产率变化示意图。Figure 1(a)(b) is a schematic diagram of the change of biodiesel yield under different temperature and catalyst conditions.
图2(a)(b)为不同醇油摩尔比对微藻生物柴油产率及密度的影响示意图。Figure 2(a)(b) is a schematic diagram of the influence of different alcohol-oil molar ratios on the yield and density of microalgae biodiesel.
图3为不同醇油摩尔比条件下的反应产物(生物柴油)密度随时间的变化图。Fig. 3 is a diagram showing the change of the density of the reaction product (biodiesel) with time under the condition of different molar ratios of alcohol to oil.
具体实施方式Detailed ways
本发明提供一种利用微藻油脂制备生物柴油的方法。其生物柴油的制备是用微藻油脂通过酯交换法获得的,其制备过程为:The invention provides a method for preparing biodiesel from microalgae oil. The preparation of its biodiesel is obtained by transesterification with microalgae oil, and its preparation process is as follows:
(1)收集微藻,然后干燥并制成藻粉;(1) collect microalgae, then dry and make algae powder;
(2)利用植物油法从藻粉中提取微藻油脂;(2) Utilize vegetable oil method to extract microalgae oil from algae flour;
(3)酯交换反应:微藻油脂中加入醇油摩尔比为25∶1~84∶1的甲醇,加热至30℃~90℃,在浓硫酸催化剂作用下,反应生成的产物经石油醚及水洗涤,离心取有机相,将有机溶剂蒸发、干燥后获得生物柴油。反应生成脂肪酸甲酯即生物柴油,并分离出副产品甘油。(3) Transesterification reaction: Add methanol with an alcohol-to-oil molar ratio of 25:1 to 84:1 to the microalgae oil, heat it to 30°C to 90°C, and under the action of concentrated sulfuric acid catalyst, the product generated by the reaction is passed through petroleum ether and Washing with water, centrifuging to take the organic phase, evaporating the organic solvent and drying to obtain biodiesel. The reaction produces fatty acid methyl ester, ie biodiesel, and the by-product glycerin is separated.
图1(a)(b)、图2(a)(b)为不同温度和催化剂条件下生物柴油产率及密度变化。通过酯交换反应条件的优化,可获得更高的产油率。利用微藻油脂通过酯交换反应,可获得高质量的生物柴油。微藻生物柴油的密度为0.864kg l-1、粘度5.2×10-4(40℃)、热值高达41MJ kg-1。这些特征与传统柴油相当,具有很好的应用前景。Figure 1(a)(b) and Figure 2(a)(b) show the biodiesel yield and density changes under different temperature and catalyst conditions. Through the optimization of transesterification reaction conditions, higher oil yield can be obtained. High-quality biodiesel can be obtained through transesterification using microalgae oil. The density of microalgal biodiesel is 0.864kg l -1 , the viscosity is 5.2×10 -4 (40°C), and the calorific value is as high as 41MJ kg -1 . These characteristics are comparable to traditional diesel, and have good application prospects.
下面例举实施例予以说明。Examples are given below for description.
实施例一不同的反应温度和催化剂用量对微藻生物柴油产率及密度的影响The influence of embodiment one different reaction temperature and catalyst consumption on microalgae biodiesel yield and density
反应条件为:30∶1醇油摩尔比,摇床转速160rpm,反应时间5h。温度分别为30℃,50℃,90℃;催化剂H2SO4用量为25%,50%,60%,100%(以原料油重量为基准)。The reaction conditions are: 30:1 molar ratio of alcohol to oil, the rotating speed of the shaker is 160 rpm, and the reaction time is 5 hours. The temperatures are 30°C, 50°C, and 90°C, respectively; the amount of catalyst H2SO4 is 25%, 50%, 60% , and 100% (based on the weight of raw oil).
在50℃条件下可获得较高的生物柴油产率,而较低密度的生物柴油则均在90℃下获得。在相同的温度条件下,催化剂用量为原料油的100%时可获得较低密度的生物柴油。最低密度(0.862)的生物柴油则是在90℃、催化剂用量为原料油的100%条件下获得的。Higher yield of biodiesel can be obtained at 50℃, while lower density biodiesel can be obtained at 90℃. Under the same temperature conditions, when the amount of catalyst is 100% of the raw oil, biodiesel with lower density can be obtained. The biodiesel with the lowest density (0.862) was obtained at 90°C and the catalyst dosage was 100% of the raw oil.
在催化剂用量为原料油的100%条件下,30℃和50℃时的产率及密度没有很大的差异。在30℃和50℃条件下的生物柴油产率分别为56%和58%,而在30℃和50℃条件下的生物柴油的密度分别为0.878和0.875(如图1所示)。因此从降低成本的角度考虑,微藻油脂的酸催化酯交换反应的反应条件为30℃、100%原料油量的催化剂用量较为合适。Under the condition that the amount of catalyst is 100% of the raw oil, there is no great difference in the yield and density at 30°C and 50°C. The yields of biodiesel at 30°C and 50°C were 56% and 58%, respectively, and the densities of biodiesel at 30°C and 50°C were 0.878 and 0.875, respectively (as shown in Figure 1). Therefore, from the perspective of cost reduction, the acid-catalyzed transesterification reaction conditions of microalgae oils and fats are 30°C, 100% of the amount of raw material oil catalyst dosage is more appropriate.
实施例二不同的醇油摩尔比对微藻生物柴油产率及密度的影响Example 2 Effects of different alcohol-oil molar ratios on microalgae biodiesel yield and density
反应条件为:温度30℃,摇床转速160rpm,催化剂H2SO4用量为100%(以原料油重量为基准),反应时间7h。The reaction conditions are as follows:
对比六种不同醇油摩尔比对产物比率及其密度的影响,在醇油摩尔比为45∶1和56∶1时可获得较高产率的生物柴油,分别是68%和63%。在这两种醇油摩尔比条件下不仅获得了较高产率的生物柴油,而且获得了低密度的生物柴油。在醇油摩尔比为45∶1和56∶1时获得的生物柴油的密度分别为0.873和0.864。醇油摩尔比为30∶1时也可获得较低密度(0.878)的生物柴油(如图2所示)。Comparing the effects of six different molar ratios of alcohol to oil on the product ratio and its density, a higher yield of biodiesel can be obtained when the molar ratio of alcohol to oil is 45:1 and 56:1, which are 68% and 63%, respectively. Under the conditions of these two molar ratios of alcohol to oil, not only a higher yield of biodiesel, but also a low density biodiesel was obtained. The densities of biodiesel obtained when the molar ratio of alcohol to oil was 45:1 and 56:1 were 0.873 and 0.864, respectively. Biodiesel with a lower density (0.878) can also be obtained when the molar ratio of alcohol to oil is 30:1 (as shown in Figure 2).
实施例三不同醇油摩尔比条件下的反应产物(生物柴油)密度随时间的变化The variation of the density of the reaction product (biodiesel) over time under the conditions of embodiment three different alcohol-to-oil molar ratios
反应条件为:温度30℃,摇床转速160rpm,催化剂H2SO4用量为100%(以原料油重量为基准)Reaction condition is:
醇油摩尔比为25∶1、70∶1和84∶1时获得的生物柴油的密度较高,且甲醇用量太大时给随后的分离带来不便。在这30∶1、45∶1和56∶1的醇油摩尔比条件下生物柴油产物的密度均随着反应时间的延长呈逐渐下降的趋势。但醇油摩尔比为56∶1时,生物柴油产物的密度在最短时间4小时内下降到最低点,获得了密度为0.864的生物柴油;而醇油摩尔比为30∶1和45∶1时,需5-7小时其产物密度才趋于最低(如图3所示)。The density of biodiesel obtained when the molar ratio of alcohol to oil was 25:1, 70:1 and 84:1 was higher, and the subsequent separation was inconvenient when the amount of methanol was too large. Under the conditions of 30:1, 45:1 and 56:1 molar ratio of alcohol to oil, the densities of biodiesel products gradually decreased with the prolongation of reaction time. However, when the molar ratio of alcohol to oil was 56:1, the density of the biodiesel product dropped to the lowest point in the shortest time of 4 hours, and biodiesel with a density of 0.864 was obtained; while the molar ratio of alcohol to oil was 30:1 and 45:1 , It takes 5-7 hours for its product density to reach the lowest level (as shown in Figure 3).
以上实验结果表明,微藻油脂的酸催化酯交换反应的最佳反应条件应为30℃、100%原料油量的催化剂用量以及56∶1的醇油摩尔比;在此条件下,4小时内可获得密度为0.864的高质量的生物柴油。The above experimental results show that the optimum reaction conditions for the acid-catalyzed transesterification of microalgae oils and fats should be 30°C, a catalyst dosage of 100% feedstock oil, and an alcohol-oil molar ratio of 56:1; under these conditions, within 4 hours High quality biodiesel with a density of 0.864 can be obtained.
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2005
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