甘油三乙酸酯超临界酯交换反应及其动力学研究

研究了在超临界条件下甘油三乙酸酯与甲醇或乙醇的酯交换反应,分别考察了超临界状态下醇油摩尔比和温度对反应的影响。实验结果表明,甲醇或乙醇与甘油三乙酸酯的摩尔比为14、反应温度为350℃、反应时间为20m in时,乙酸甲酯或乙酸乙酯的收率分别达100%和60%。对超临界状态下动力学的研究结果表明,甘油三乙酸酯与甲醇或乙醇的酯交换反应为拟一级反应,在相同的反应条件下,采用甲醇时酯交换反应速率比用乙醇时快,相应的甘油三乙酸酯的转化率也高;甘油三乙酸酯在超临界甲醇或乙醇中酯交换反应的表观活化能分别为58.7 kJ/mol和75.1 kJ/mol,甘油三乙酸酯与甲醇酯交换反应的活化能低于与乙醇酯交换反应的活化能,表明碳链短的醇更易进行酯交换反应。     

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%。     

Densities and excess molar volumes of mixtures containing diesel,biodiesel and alkanols at temperatures from 288.15 to 313.15 K

The present work is focusing on the synthesization and physico-chemical properties of Jatropha curcas biodiesel with diesel and alcohols.The densities of binary diesel (2)+1-alkanols (C_3 or C_4)(3) and ternary Jatropha curcas biodiesel (1)+diesel (2)+1-alkanols (C_3or C_4)(3) blends have been reported over full range of composition at temperatures within range 288.15 to 313.15 K.Also densities of Jatropha curcas biodiesel (1)+diesel or 1-alkanols (C_3 or C_4)(2) blends have been measured at 313.15 K.Excess molar volumes,V~E,V~E_(123)of binary and ternary blends were calculated from the measured data and the derived properties were correlated to composition using Redlich–Kister equation.A reasonable agreement was found between the measured and estimated values.Further,densities and excess molar volumes data were reasoned to discuss molecular interactions taking into consideration effect of composition and temperature.     

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.     

生物柴油制备方法的应用研究进展

生物柴油以其优良的环境友好性和可再生性引起广泛关注,但较高的生产成本是其商业化生产和应用的障碍之一。综述了生物柴油的化学转酯化法和以游离脂肪酶、固定化脂肪酶、全细胞为催化剂的生物转酯化法的工业研究进展,同时还指出了采用生物转酯化法制备生物柴油时面临的一些问题。     

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.     

The pseudo-single-phase,base-catalyzed transmethylation of soybean oil

The base-catalyzed transmethylation of soybean oil has been studied under conditions whereby the reaction starts as a single phase, but later becomes two phases as glycerol separates. Methanol/oil molar ratios of 6∶1 were used at 23°C. The catalysts were sodium hydroxide (0.5, 1.0, and 2.0 wt%), potassium hydroxide (1.0 and 1.4 wt%), and sodium methoxide (0.5, 1.0, and 1.35 wt%), all concentrations being with respect to the oil. Oxolane (tetrahydrofuran) was used to form a single reaction phase. The reactions deviated from homogeneous kinetics as glycerol separated, taking with it most of the catalyst. When 1.0 wt% sodium hydroxide was used, the methyl ester content reached 97.5 wt% after 4 h, compared with 85–90 wt% in the two-phase reaction. Sodium hydroxide (1.0 wt%), sodium methoxide (1.35 wt%), and potassium hydroxide (1.4 wt%) gave similar results, presumably because the same number of moles was used. The ASTM biodiesel specification for chemically bound glycerol was achieved after only 3 min when 2.0 wt% sodium hydroxide was used. However, the standard was not achieved after 4 h when 1.0 wt% sodium hydroxide was used, the MG content being 1.1–1.6 wt%. The use of 2.0 wt% catalyst is commercially impractical.     

可再生的绿色能源——生物柴油

20世纪人类使用的能源主要有三种:原油、天然气和煤炭。而另一个值得重视的新能源是可再生的绿色能源——生物能。在各种可再生能源中,生物质是贮存的太阳能,更是一种唯一可再生的碳源,可转化成常规的固态、液态和气态燃料。生物燃料作物作为未来的一种新能源,与其他能源比有许多优点,环保、可再生是生物能源最大的优势。生物柴油是近年来发展迅速并规模化使用的生物替代能源。生物柴油的制备主要有酶催化、酸催化、碱催化、酸—碱催化、超临界等方法。     

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。