利用高酸值餐饮废油脂制备生物柴油

以高酸值餐饮废油脂为原料,在酯化反应后再经两步酯交换反应制备生物柴油。在酯化反应中添加吸水剂可降低油脂的酸值,经一次酯化反应即可将油脂的酸值降至2m g/g左右,满足酯交换反应的要求。考察了酯化反应中吸水剂的添加方式、种类及其用量对酯化反应的影响,以及酯交换催化剂的种类及用量对脂肪酸甲酯(FAME)收率和产物组成的影响。实验结果表明,以凹凸棒土为吸水剂(用量为餐饮废油脂中游离脂肪酸质量的3%),且在酯化反应30m in时加入,酯化效果较好;以质量比为1∶1的NaOH和KOH混合物为催化剂进行两步酯交换反应时,催化剂的最佳用量依次为1.00%和0.75%(质量分数,基于油脂的质量),FAME收率最高达到96.33%。     

Synthesis of Biodiesel from Soybean Oil using Heterogeneous KF/ZnO Catalyst

Biodiesel was produced by transesterification of soybean oil with methanol using ZnO loaded with KF as a solid base catalyst. It was found that the catalyst with 15 wt.% KF loading and calcined at 873 K showed the optimum activity. XRD, IR and Hammett indicator method were employed for the catalyst characterization. The results showed the activity of the catalysts was correlated with their basicity. The influence of various reaction variables on the conversion was also discussed.     

Oxidative stability of soybean oil fatty acid methyl esters by oil stability index (OSI)

Biodiesel, an alternative diesel fuel derived from transesterification of vegetable oils or animal fats, is composed of saturated and unsaturated long-chain FA alkyl esters. During long-term storage, oxidation caused by contact with air (autoxidation) presents a legitimate concern with respect to monitoring and maintaining fuel quality. Extensive oxidative degradation may compromise quality by adversely affecting kinematic viscosity, acid value, or PV. This work examines the oil stability index (OSI) as a parameter for monitoring the oxidative stability of soybean oil FAME (SME). SME samples from five separate sources and with varying storage and handling histories were analyzed for OSI at 60°C using an oxidative stability instrument. Results showed that OSI may be used to measure relative oxidative stability of SME samples as well as to differentiate between samples from different producers. Although addition of α-tocopherol or TBHQ increased OSI, responses to these antioxidants varied with respect to SME sample. Variations in response to added antioxidant were attributed to aging and other effects that may have caused oxidative degradation in samples prior to acquisition for this study. Results showed that OSI was more sensitive than iodine value in detecting the effects of oxidative degradation in its early stages when monitoring SME during storage.     

棉籽油间歇式酯交换反应动力学的研究

生物柴油(棉籽油甲酯)可以由棉籽油与甲醇在催化剂KOH存在下通过酯交换反应制得。故对棉籽油间歇式酯交换反应动力学进行了研究,并考察了反应温度和催化剂浓度对产物棉籽油甲酯浓度的影响。用液相色谱法分析棉籽油的组成;用气相色谱法分析产物中棉籽油甲酯的含量。由实验数据绘制的动力学曲线得到酯交换反应在开始阶段为准二级反应,以后紧接转为一级反应和零级反应,与文献报导的棕榈油酯交换反应动力学结果一致。由实验数据求出酯交换反应在开始阶段的动力学参数,35℃、45℃时的反应速率常数分别为0.9179Lmol-1min-1和1.049Lmol-1min-1,酯交换反应的活化能为10.88kJmol-1。根据实验结果得到棉籽油酯交换反应的最佳反应温度为45℃,最佳催化剂为1.1%KOH。     

Phase behavior of the base-catalyzed transesterification of soybean oil

Biodiesel is made by the transesterification of vegetable oils to form alkyl FA esters. High levels of conversion (>99%) are required to lower the total concentration of free and chemically bound glycerol to that allowed by the ASTM standard (0.240 wt%) for biodiesel. A polar dye was used to visualize the phase behaviors in methanolysis, ethanolysis, and butanolysis. The dye was more strongly colored in more polar phases. Methanolysis and ethanolysis reactions commenced as two phases (alcohol and oil), then formed emulsions, and ended as two phases as glycerol-rich phases separated. Ethanolysis was more easily initiated by mixing than was methanolysis. Ethanolysis also exhibited a much longer emulsion period and slower glycerol separation. The glycerol-rich phase was smaller in volume in ethanolysis than in methanolysis. Butanolysis remained one phase throughout, and no polar phase existed at any time. The results are consistent with the known phase compositions in these reactions. The concentrations of MG, DG, and TG in the products with time in stirred reactions were consistent with the observed phase behavior in the dye experiments.     

CO2 process intensification of algae oil extraction to biodiesel

Algae-to-biodiesel processes are hindered by high costs and low energy return on investment.^1,2. Herein, three foci in research improve algae-to-biodiesel processes by: (1) reducing high installation and energy costs in the CO₂ sequestration, cultivation, and harvesting stages; (2) improving oil extraction and biodiesel generation; and (3) increasing utilization of the proteins in lipid-extracted biomass (e.g., for animal feed), as well as the omega-3 fatty acids for nutraceuticals and food supplements. A process is introduced that uses carbon dioxide to aid in all three of these foci. CO₂ is used first in the form of microbubbles to lyse algae cell walls, releasing triglyceride oils. CO₂ also aids with transesterification of these triglycerides using methanol. At low temperatures (353.15–368.15 K) and intermediate pressures (5–10 MMPa), carbon dioxide causes methanol to dissolve partially in the triglyceride phase and triglyceride to dissolve partially in the methanol phase, increasing the transesterification reaction rate. Due to the nondestructive nature of these processes, other metabolites can also be harvested providing improvements in both mass and economic efficiency with an overall sharp reduction in the modeled price of biodiesel.     

Improving the cold flow properties of biodiesel from waste cooking oil by ternary blending with bio-based alcohols and diesel from direct coal liquefaction

The utilization and popularization of biodiesel are always limited by its poor cold flow properties. Both bio-based alcohol and diesel from direct coal liquefaction (DDCL) has potential to enhance the cold flow properties of biodiesel. In this study, ternary blends of waste cooking oil biodiesel (BWCO) with DDCL and bio-based ethanol (ET) or 1-butanol (BT) were conducted to improve the cold flow properties of biodiesel. The pour point (PP), cold filter plugging point (CFPP), and cloud point (CP) of BWCO-ET, BWCO-BT, and BWCO-DDCL binary blends, and BWCO-ET-DDCL and BWCO-BT-DDCL ternary blends were comparatively assessed. Ternary phase diagrams were also applied to analyze the blending effect of the three components on the cold flow properties of biodiesel. Results showed that both DDCL, ET, and BT can remarkably enhance the cold flow properties of BWCO. When the ternary blends contain 20 vol.% BWCO and less than 40 vol.% ET or BT, DDCL together with ET or BT exerted positive effects on enhancing the low-temperature flow properties of BWCO, especially on the CP and CFPP. For ternary blends in 20:10:70 blending ratio, BWCO-BT-DDCL exhibited the lowest PP, CFPP, and CP of −23, −19, and −17°C, respectively. The crystallization behavior and crystal morphology of blended fuels are also observed via a polarizing optical microscope, and find that DDCL together with BT in biodiesel can effectively retard the aggregation of large crystals and inhibit crystals growth.     

生物柴油酯交换反应器的一种控制策略研究

生物柴油生产过程具有小批量、多品种特性,使得模型具有不确定性,因此,机理建模对生物柴油生产过程仿真研究具有重要意义.同时,鉴于生物柴油生产过程中存在高度的非线性、多变量耦合性、条件约束性等诸多问题,采用模型预测算法作为控制策略.实验结果表明：合理的模型预测控制器设计能有效地提升酯交换器的性能.     

生物柴油副产物下层甘油液的组成分析及其分离

分析了菜籽油和大豆油碱催化酯空换法制备生物柴油副产物下层甘油液的主要成份。下层甘油液中主要古甘油、甲醇和脂肪酸皂以及少量的脂肪酸甲酯和游离碱。探索了分离方法。获得的甲醇和脂肪酸可用于生物柴油生产和其它产品的原料，获得的甘油音量达到分析纯要求。     

生物柴油及其原料中水分含量的测定

通过比较卡尔费休法和烘箱法认为卡尔费休法和烘箱法都适合于植物油中水分含量的测定,而卡尔费休法适合于生物柴油中水分含量的测定。