油酸甲酯合成反应动力学研究

油酸甲酯是一种重要的化工原料,因现行生产工艺存在污染环境、腐蚀设备、反应转化率较低等问题,使其生产受到了一定制约,为此,提出了一种无催化"两步法"合成油酸甲酯的工艺路线。文中在"两步法"工艺路线的基础上进一步研究了油酸甲酯合成反应动力学。采用积分法分析了在293,298,303,308,313 K下的实验数据,结果表明二步反应均符合二级反应特征,反应遵循四面体机理,并得到了不同温度下的动力学方程式。根据得到的不同温度下的反应速率常数确定了二步反应的活化能分别为121.6 kJ/mol和115.2 kJ/mol,频率因子为2.76×1019和4.03×1018。在实验293—313 K温度范围内,通过实验对得到的动力学方程进行验证,得到的实验值与动力学方程计算值相符合,说明得到的动力学方程是可靠的,为"两步法"合成油酸甲酯的工业放大提供了理论依据。     

生物质热解特性和动力学研究

利用热重分析对在氮气气氛下不同升温速率的马尾松生物质原料热失重行为进行了研究。由失重和失重速率曲线分析可知,生物质热解过程分为三个阶段。根据热重实验数据建立动力学热解模型,运用Popescu法从22种动力学机理函数中寻求裂解的最概然机理函数并计算裂解的动力学参数。结果表明,Zhuralev,Lesokin和Tempelmen(Z-L-T)方程为最概然机理函数。     

生物质催化热解特性和动力学研究

利用热分析技术对氮气气氛下不同升温速率下马尾松生物质试样的热解过程和以Na2CO3为催化剂的催化热解过程进行了研究。结果表明,Na2CO3催化剂可使生物质的主要热解区向低温区移动,而最大失重速率减少。根据热重实验数据,运用Popescu法对马尾松热解和催化热解动力学进行了研究。结果表明,Z-L-T方程为热解和催化热解的最概然机理函数,并计算出其相应的热解动力学参数。     

基于热重-红外联用技术分析油酸的热解特性及动力学分析

利用热重红外联动技术（TG-DTG-FTIR）研究了橡胶籽油中的单不饱和游离脂肪酸油酸组分在不同升温速率（5℃/min、10℃/min、20℃/min、30℃/min）下的热解特性。然后,用多元线性回归法对油酸非等温热解所得到的特性参数进行研究并计算,求得不同升温速率下对应的反应级数、活化能和指前因子,并对不同升温速率下油酸热解反应活化能和指数前因子作线性拟合。结果表明：油酸热解过程主要可分为0～268℃和268～300℃两个阶段,由红外谱图特征峰的分析可知,不同升温速率下,在油酸热解的阶段内均出现了水蒸气、CH₄、CO₂和CO这4种主要气体挥发分。随着升温速率的增大,油酸热解的最大失重速率随之增大,热解区间也向着高温段移动,同时计算在升温速率从5～30℃/min的过程中,反应级数n=1时,热解反应活化能由105.57kJ/mol降低至93.99kJ/mol,指数前因子由6.99×10⁶降低至6.7×10⁵;n≠1时,热解反应活化能由102.45kJ/mol降低至93.38kJ/mol,指数前因子由3.13×10⁶降低至2.97×10⁴,反应活化能和指数前因子随升温速率的增大出现明显减小。通过对不同升温速率下油酸热解反应的活化能和指数前因子进行线性拟合后发现,两者间具有较好的补偿效应。     

油酸甲酯连续合成工艺及其动力学研究

在固定床反应器中,以阳离子交换树脂为催化剂,油酸与甲醇液液并流反应制备油酸甲酯。考察了反应各影响因素,获得较适工艺条件为:催化剂装载量20 g,醇酸摩尔比2∶1,反应温度60℃,停留时间40 min。在此条件下,油酸转化率可达99.43%。对油酸与甲醇的反应动力学进行了研究,以拟均相模型对实验数据进行拟合,得出30℃、40℃、50℃、60℃下的正、逆反应速率常数。反应速率随温度的升高而加快,二者关系符合Arrhenius方程,该反应的活化能为60.687 kJ/mol。     

内蒙和印尼褐煤的热解特性及动力学分析

采用非等温热重法对内蒙和印尼两种褐煤的热解特性进行了研究,探讨了升温速率对热解过程的影响,然后用Doyle积分法对褐煤的热解进行了动力学分析.研究表明,两种褐煤的热失重过程都分为四个阶段,第一阶段(室温～200℃)为干燥脱气阶段,其他三段为煤热解阶段.升温速率对热失重过程略有影响,通过动力学分析所得的热解动力学参数能很好地反映煤的热解情况.     

西部煤的热解特性及动力学研究

采用热重和红外分析法从升温速率与样品粒径的相关性等方面对平朔煤和神东煤的热解特性进行研究,并从动力学上进行分析.结果表明,随升温速率增大,煤样热解反应的初始温度、终止温度以及最大失重速率对应的温度都逐渐升高,但对粒径较小的煤样来说,这些特性温度增加的幅度较大,而最大失重率没有表现出一定的规律性;煤样粒径对热解也有一些影响,但最大失重速率与样品粒径的关系不大.随升温速率增大,热解活化能和频率因子呈现出先增大后减小的趋势.     

芦苇秆热解特性及动力学分析

为了充分利用芦苇秆生物质能源,以不同升温速率对芦苇秆进行热重实验,分别运用Coats-Redfern（CR）法、Flynn-Wall-Ozawa（FWO）法、Kissinger-Akahira-Sunose（KAS）法计算芦苇秆热解动力学参数,并利用主函数图法确定反应机理和动力学。结果表明：芦苇秆热解可分为4个阶段,其中190~400℃为主要热解阶段。在此阶段,将3种方法计算所得转化率（α）与实验数据进行对比,发现当温度大于250℃时,Coats-Redfern法计算值与实验数据偏差较大,而Flynn-Wall-Ozawa法与Kissinger-Akahira-Sunose法在整个阶段内吻合度较高。由主函数图法可知芦苇秆热解最佳反应机理为随机成核,反应级数为2。对比残差平方和发现,Kissinger-Akahira-Sunose法相比于Flynn-Wall-Ozawa法更适合计算芦苇秆热解动力学参数,计算的表观活化能随转化率的增大呈先增大后减小的趋势,并在转化率为50%时达到最大值286.9 kJ/mol。     

长白松热解特性及热解动力学研究

为获取长白松的热解特性,预防森林火灾发生,以长白松的树枝、球果、树皮和松针作为研究对象进行热解过程分析,并采用Coats-Redfern法进行热解动力学分析,以球果为研究对象探究各种因素对长白松热解的影响。实验结果表明：4种材料的热解过程均可分为4个阶段,其中主要失重阶段的质量损失率为60%左右。升温速率越大,热解越不充分,并且存在热滞后现象,25℃/min时质量损失率最小(80.34%);粒径大小对TG、DTG曲线影响较小,粒径越小,内外部受热更均匀,因此0.20 mm粒径的材料质量损失率最大(91.18%);氮气气氛下主要失重阶段有一个失重峰,而在高纯空气气氛下有两个失重峰,且长白松球果在高纯空气中热解时间更长,热解更充分,促进作用更强,质量损失率为98.14%。热解动力学分析结果显示：4种材料的最佳机理函数为“三维扩散”,活化能最大的是树枝(157.04 kJ/mol),最小的是松针(98.19 kJ/mol),球果的活化能为148.08 kJ/mol,树皮的活化能为115.04 kJ/mol,因此,要格外注意对松针和树皮的防火工作。     

竹材热解失重动力学模型研究

采用热重分析仪在温度范围313～873 K和N2气流保护下,以不同升温速率(10、20、30、50 K·min-1)对两种竹材(#1 和#2)进行了热解失重动力学研究,并分别采用非模型动力学法(model-free kinetics,MFK)和模型拟合法(model-fitting method)分析了热重分析结果,结...     

磷钨酸铋催化合成油酸甲酯

以磷钨酸铋为催化剂,对油酸和甲醇反应合成油酸甲酯进行了研究,考察了反应时间、催化剂用量、醇酸摩尔比、催化剂重复使用性等因素对油酸甲酯收率的影响.实验结果表明反应的最佳条件为:油酸用量为0.1 mol,醇酸摩尔比为1.4,催化剂磷钨酸铋用量为1.5 g,反应时间为4h,酯收率达93.4％,催化剂重复使用五次催化性能未见明...     

Production of Methyl Oleate in Reactive‐Separation Systems

The esterification of oleic acid and methanol using sulfuric acid as a homogeneous catalyst is studied in reactive‐separation systems. The conversion of the free fatty acid was investigated in two different experiments with the molar ratio of methanol/oleic acid, amount of catalyst, temperature, and reaction time as variables. The conversion of the free fatty acid was found to depend strongly on the molar ratio of methanol/oleic acid. The reaction time had a direct effect on the conversion of the free fatty acid, and this conversion decreased with higher temperature. These results were valuable for a preliminary study on biodiesel production, using an acid homogeneous catalyst in a reactive dividing‐wall distillation column.     

废弃汽车塑料保险杠材料热解特性及动力学研究

通过红外光谱分析及热重分析可知,汽车塑料保险杠的主要成分为聚丙烯和三元乙丙橡胶。应用热重-红外联用技术考察了其热解特性,采用Doyle积分法分析了塑料保险杠在不同升温速率下的热解规律。     

Ti(SO4)2/C催化合成硬脂酸甲酯的研究

研究了Ti(SO4)2/C在硬脂酸与甲醇酯化中的催化性能，结果表明，Ti(SO4)2/C在该反应中具有很好的催化性能，并得到了合成硬脂酸甲酯的新工艺条件；催化剂用量（硬脂酸质量分数）为5％；醇酸摩尔比为6：1，反应温度70℃，反应时间3h，优化条件，硬脂酸的酯化率达98％。     

Pyrolysis Kinetics of Wood and Wood Components

The kinetics of pyrolysis decomposition reactions of wood and its components are described employing mathematical modeling tools for first and n^th order reactions, autocatalytic reactions, and parallel first order and autocatalytic reactions. Secondary reactions may accelerate the reaction rate and a new autocatalytic reaction model was developed to describe this specific behavior.     

Synthesis of Chloro Alkoxy and Alkoxy Derivatives of Methyl Oleate

Vegetable oil based lubricants typically have improved lubricity and biodegradability over their mineral oil based counterparts. However, vegetable oil lubricants often fail to meet the performance standards of mineral based oils with respect to cold temperature and resistance to oxidation. Olefins are an oxidatively weak point for vegetable based compounds. Removal of the olefin in a vegetable based lubricant through functionalization may increase resistance to oxidation. If the added functionality also causes branching of the alkyl chain, cold temperature properties may be improved. Any chemical modifications considered must be scalable and cost-effective to be useful in a commercial application. In this study, methyl oleate was functionalized into a chloro alkoxy derivative. Sodium hypochlorite (household bleach) and calcium hypochlorite were both used to generate hypochlorous acid in situ. Hypochlorous acid and a series of alcohols (methanol, ethanol, and butanol) were reacted with methyl oleate to make chloro alkoxy compounds in 29.8–77.9 % yields. In an effort to make a branched saturated ether we removed the chlorine moiety of the chloro alkoxy compounds. Dehalogenation was achieved under basic conditions over a Pd/C catalyst in 2-propanol. Reaction times increased substantially as the size of the adjacent alkoxy group increased. The reaction rate could be improved by heating the reactions above 100 °C in a pressure reactor. Increased reaction temperature also resulted in an increase in ketone side products from the competing elimination reactions. Saturated ether yields were 4.1–43.2 %.     

油酸甲酯影响柴油机油清净性模拟研究

在柴油机油中加入不同比例的油酸甲酯,采用变温成漆板模拟实验,研究油酸甲酯对柴油机油清净性的影响,结果表明,油酸甲酯明显加速了柴油机油氧化变质。随着油酸甲酯加入比例提高、铝板板温增加,柴油机油清净性随之变差。不同比例的油酸甲酯对不同质量等级的柴油机油清净性影响有所不同,其由大到小的顺序为10%油酸甲酯+CD 15W/40,5%油酸甲酯+CD 15W/40,CD 15W/40,10%油酸甲酯+CF-4 15W/40,5%油酸甲酯+CF-4 15W/40,CF-4 15W/40。     

Proton Nuclear Magnetic Resonance-Based Method for the Quantification of Epoxidized Methyl Oleate

Epoxidized methyl esters (EMO) with their high oxirane ring reactivity, acts as a raw material in the synthesis of various industrial chemicals including polymers, stabilizers, plasticizers, glycols, polyols, carbonyl compounds, biolubricants etc. EMO has been generally quantified by the gas chromatography (GC) and high-performance liquid chromatography (HPLC) techniques. Taking into the account of the limitations of these techniques, two qHNMR-based equations have been proposed for the quantification of EMO in the mixture of EMO and methylesters (MO). The validity of the proposed method was determined using standard mixtures of MO and EMO having different molar concentrations. The developed equations have been applied on the samples of EMO prepared from oleic acid in two-step process viz., esterification followed by epoxidation. The qHNMR-based EMO quantification showed acceptable agreement with the results obtained from HPLC analysis.     

Pyrolysis products of uncoated printing and writing paper of MSW

Uncoated printing and writing paper, one of the principal waste papers in Taiwan, was pyrolyzed with a thermogravimetric analysis (TGA) reaction system. The pyrolysis experiments were carried out in nitrogen environment at a constant heating rate of 5 K min⁻¹. The gaseous products and the residues were collected at room temperature (300 K) and analyzed by gas chromatography (GC) and elemental analyzer, respectively. The major gaseous products investigated included non-hydrocarbons (H₂, CO, CO₂, and H₂O) and hydrocarbons (C_1-3, C₄, C₅, C₆, 1-ring, C_10-12, levoglucosan, C_13-15, and C_16-18). The cumulated masses and the instantaneous concentrations of gaseous products were obtained under the experimental conditions. The yields of non-hydrocarbon gases and of hydrocarbon gases were about 10.46 and 0.49% at 623 K, 33.68 and 0.89% at 700 K, 64.52 and 1.05% at 788 K, and 79.10 and 1.63% at 938 K, respectively. The estimation of the mass of tar, yielded at various pyrolysis temperatures was also made. The results of this study might be useful for the design of pyrolysis process as well as for determining the pyrolysis mechanisms of the uncoated printing and writing paper.     

Interesterification of Soybean Oil and Methyl Stearate Catalyzed by Guanidine‐Functionalized SBA‐15 Silica

The main purpose of this study was to develop a heterogeneous interesterification catalyst for the modification of edible oils to enhance their physicochemical and functional performances. To achieve this, 1,3‐dicyclohexyl‐2‐octylguanidine was covalently immobilized on the SBA‐15 (Santa Barbara Amorphous 15) material and then used as solid catalysts for the interesterification between soybean oil and methyl stearate. The characterization of the guanidine‐functionalized SBA‐15 material included Fourier transform infrared spectra, scanning electron microscopy, elemental analysis, and nitrogen adsorption–desorption techniques. It was shown that the solid base catalyst could efficiently catalyze the interesterification reaction. After the interesterification, the fatty acid profiles and triacylglycerol compositions of interesterified products were substantially varied. The influence of interesterification parameters, such as the substrate ratio, reaction time, reaction temperature and catalyst loading, on the interesterification reaction was investigated regarding the percentage of stearic acid in interesterified triacylglycerols. The stearic acid percentage of 27.9 % was achieved at 100 °C within 4 h when the methyl stearate/soybean oil molar ratio of 6:1 was employed. The catalyst could be recovered easily by filtration and reused without significant loss of activity.