Synthesis of Biodiesel from Palm Oil in Capillary Millichannel Reactor: Effect of Temperature,Methanol to Oil Molar Ratio,and KOH Concentration on FAME Yield

Application of microtube reactor for the continuous synthesis of biodiesel has been widely studied due to excellent performance in liquid-liquid phase reaction. In order to commercialize biodiesel production, integration of microtube reactor is highly recommended. Therefore, in this study, synthesis of biodiesel was carried out in capillary millichannel reactor with inner diameter of 1.59 mm using methanol and potassium hydroxide (KOH) as base catalyst with palm oil as a feedstock. The influences of reaction temperature, methanol to oil molar ratio, and KOH concentration on the production of fatty acid methyl ester (FAME) were examined. The highest FAME yield was achieved at 60 ˚C with 23:1 methanol to oil molar ratio and 5 wt% of KOH concentration.     

Biodiesel Production from Waste Cooking Oil over Mesoporous SO42-/Zr-SBA-15

Biodiesel production from waste cooking oils over SO₄^2-/Zr-SBA-15 catalyst was successfully carried out and investigated. SO₄^2-/Zr-SBA-15 catalyst was prepared by one-step process using anhydrous zirconium nitrate as zirconium resource, and endowed with the strong Lewis acid sites formed by supporting the zirconium species onto the SBA-15 surface. The asprepared SO₄^2-/Zr-SBA-15 showed excellent triglyceride conversion efficiency of 92.3% and fatty acid methyl esters (FAME) yield of 91.7% for the transesteriffication of waste cooking oil with methanol under the optimized reaction conditions: the methanol/oil molar ratio of 30, the reaction temperature of 160 oC, the reaction time of 12 h and 10wt% of catalyst. It was noticed that the as-prepared SO₄^2-/Zr-SBA-15 materials with the higher area surface of mesoporous framework and the surface acidity displayed excellent stability and reusability, maintaining high FAME yield of (74±1)% after seven runs of reaction.     

Alkali Hydrothermal Synthesis of Na0.1Ca0.9TiO3 Nanorods as Heterogeneous Catalyst for Transesterification of Camelina Sativa Oil to Biodiesel

Orthorhombic perovskite Na_0.1Ca_0.9TiO₃ nanorods were synthesized at low calcination temperature via alkali hydrothermal synthesis. The synthesized nanorods exhibits a square based prism morphology, with a width and length of 200–500 nm and 2–3 μm respectively. The structural, textural and basic characteristics of the catalyst were examined by SEM, TEM, XRD and BET. The growth direction of the nanorods was confirmed to be along the long symmetry [110] zone axis and the exterior surfaces are found to be polar (110) and (002) with either Ti or Ca exposed in those facets. The catalytic activity of the nanorods was investigated for the transesterification of the low-input Camelina Sativa oil and methanol to give the fatty acid methyl ester (FAME). Effects of important reaction parameters such as methanol to oil molar ratio, catalyst dosage, reaction temperature and reaction time on oil conversion were examined. Optimized biodiesel yield of 93 % was achieved with catalyst dosage of 6 % w/w, methanol to oil molar ratio of 36:1 at reaction temperature of 60 °C for 8 h.     

Fast Biodiesel Production with One-Phase Reaction

The feasibility of fatty acid methyl ester (FAME) as a co-solvent used to increase the mass transfer between oil and methanol was investigated. FAME, as the co-solvent, does not require additional separation after the reaction because it is the end product of the reaction. To examine intermediate phenomena during the transesterification of soybean oil, the agitation speed was controlled at a slow rate. When the molar ratio of oil to methanol was 1:6 at 0.8wt.% of KOH to oil, oil was at the bottom layer, and methanol and the catalyst were at the top layer. Under the slow agitation process, the contact surface became initially darkened with the production of FAME and glycerol. After a few minutes, the entire top layer became dark. The top layer, containing methanol, KOH, FAME, and glycerol, fell to the bottom layer and then formed the one-phase system. When 0, 5, and 10 wt.% of FAME to oil was initially introduced to the reaction mixture, the FAME content rapidly increased with the FAME concentration level. After forming the one-phase system, the rate of increase of the FAME content was very slow. The time required for the formation of the one-phase system decreased with the amount of FAME and KOH and with temperature.     

Transesterification of palm oil using supercritical methanol with co-solvent HCFC-141b

The transesterification of palm oil in supercritical methanol has been investigated without using any catalyst. HCFC-141b was used as co-solvent to reduce the molar ratio of methanol to palm oil under the milder conditions. The reaction was carried out in a flow-type tubular reactor. The residence time was fixed at 40 min. When the molar ratio of methanol to palm oil was set to 20:1 at 325 °C and 35 MPa, the optimum molar ratio of methanol to co-solvent was found to be 20:1. Addition of HCFC-141b increased FAME production even at the lower molar ratio of methanol to palm oil. In addition, a similar FAME content was obtained under the milder conditions (5 MPa lower pressure) compared with conditions without co-solvent at higher pressure. The role of HCFC-141b in the transesterification reaction under supercritical conditions was investigated.     

钾霞石固体碱催化豆油酯化反应制备生物柴油

采用共沉淀法制备了钾霞石,用于催化豆油和甲醇酯化反应,在煅烧温度1 200℃,得到单一的钾霞石物相.钾霞石表面多孔,孔径分布为0.2到1.0 μm,有利于反应物分子的内扩散和接触活性位;同时对反应温度、反应时间、催化剂用量以及催化剂Li含量进行了系统研究.反应温度120 ℃,醇油摩尔比12:1,反应时间2 min,催化...     

Fatty acid methyl ester production from acid oil using silica sulfuric acid: Process optimization and reaction kinetics

Conversion of high free fatty acids (FFA) containing acid oil (AO) to fatty acid methyl esters (FAME) using silica sulfuric acid (SSA) as a solid acid catalyst was investigated. Process parameters such as reaction temperature, reaction time, catalyst loading, and methanol to oil molar ratio were optimized using the Taguchi orthogonal array method. Maximum FFA conversion (97.16 %) was achieved under the optimal set of parameter values viz. 70°C, 4 mass % catalyst loading, and 1: 15 oil to methanol molar ratio after 90 min. SSA was reused three times successfully without a significant loss in activity. Biodiesel produced from AO met the international biodiesel standards. Determination of kinetic parameters proved that the experimental results fit the pseudo first order kinetic law.     

Clean synthesis of biodiesel over solid acid catalysts of sulfonated mesopolymers

FDU-15-SO₃H, a solid acid material prepared from the sulfonation of FDU-15 mesoporous polymer, has been demonstrated to serve as an efficient catalyst in the esterification of palmitic acid with methanol as well as in the transesterification of fatty acid-edible oil mixture. FDU-15-SO₃H achieved an acid conversion of 99.0% when the esterification was carried out at 343 K with a methanol/palmitic acid molar ratio of 6:1 and 5 wt% catalyst loading. It was capable of giving 99.0% yield of fatty acid methyl esters (FAME) when the transesterification of soybean oil was performed at 413 K and the methanol/oil weight ratio of 1:1. FDU-15-SO₃H was further applied to the transesterification/esterification of the oil mixtures with a varying ratio of soybean oil to palmitic acid, which simulated the feedstock with a high content of free fatty acids. The yield of FAME reached 95% for the oil mixtures containing 30 wt% palmitic acid. This indicated the sulfonated mesopolymer was a potential catalyst for clean synthesis of fuel alternative of biodiesel from the waste oil without further purification.     

Comparison and optimisation of biodiesel production from <Emphasis Type="Italic">Jatropha curcas</Emphasis> oil using supercritical methyl acetate and methanol

In this study, biodiesel has been successfully produced by transesterification using non-catalytic supercritical methanol and methyl acetate. The variables studied, such as reaction time, reaction temperature and molar ratio of methanol or methyl acetate to oil, were optimised to obtain the optimum yield of fatty acid methyl ester (FAME). Subsequently, the results for both reactions were analysed and compared via Response Surface Methodology (RSM) analysis. The mathematical models for both reactions were found to be adequate to predict the optimum yield of biodiesel. The results from the optimisation studies showed that a yield of 89.4 % was achieved for the reaction with supercritical methanol within the reaction time of 27 min, reaction temperature of 358°C, and methanol-to-oil molar ratio of 44. For the reaction in the presence of supercritical methyl acetate, the optimum conditions were found to be: reaction time of 32 min, reaction temperature of 400°C, and methyl acetate-to-oil molar ratio of 50 to achieve 71.9 % biodiesel yield. The differences in the behaviour of methanol and methyl acetate in the transesterification reaction are largely due to the difference in reactivity and mutual solubility of Jatropha curcas oil and methanol/methyl acetate.     

CaO-MgO@CoFe_2O_4磁性固体碱的制备及其大豆油酯交换反应催化性能

以草酸盐为前驱体采用两步法制备了一种以CaO-MgO作为活性组分,以CoFe_2O_4作为磁核的磁性固体碱催化剂,并用于大豆油与甲醇的酯交换反应合成生物柴油。对制备的磁性固体碱催化剂进行了磁滞回线、X-射线衍射(XRD)、CO_2-TPD及透射电镜(TEM)表征。考察了不同核壳物质的量比、焙烧温度、反应温度、反应时间、醇油物质的量比以及催化剂用量等因素对大豆油转化为生物柴油产率的影响。结果表明,采用核壳物质的量比为1∶6、焙烧温度为700℃所制备的CaO-MgO@CoFe_2O_4催化剂,当醇油物质的量比为12、催化剂用量为大豆油质量的1.0%时,在65℃下反应时间3 h,生物柴油收率高达97.1%。该催化剂具有较好的重复利用性能,重复利用四次后生物柴油的收率仍可达90%。     

超声作用下KF/CaO催化酯交换反应制备生物柴油

等体积浸渍法制备了KF/CaO固体碱催化剂,用于催化大豆油与甲醇酯交换反应制备生物柴油,在反应体系中引入超声作为辅助条件。研究表明,KF/CaO催化活性高。在超声的辅助作用下,酯交换反应速率加快,生物柴油的收率提高。实验考察了反应条件对产品中脂肪酸甲酯含量的影响。醇油摩尔比为12∶1,反应温度65℃,催化剂与大豆油的质量比为3%,反应1 h,超声频率20 kHz,超声声强1.01 W/cm2,在此反应条件下,产品中脂肪酸甲酯的质量分数达到99.6%。     

Coupling transesterifications for no-glycerol biodiesel production catalyzed by calcium oxide

In this study, a method consisting in coupling transesterifications for no-glycerol biodiesel production catalyzed by CaO was put forward. The transesterification between rapeseed oil and methanol was greatly improved by integrating glycerol and dimethyl carbonate (DMC) transesterification. From this result, it was found that the high fatty acid methyl ester (FAME) yield of 92.6% (with ultra-traces of glycerol as a by-product) was obtained at 65 °C under normal pressure, which is as high as the previously reported supercritical DMC method for no-glycerol biodiesel production at a reaction temperature of 350 °C and under pressures up to 17.8 MPa. Moreover, this new method has high water tolerance, and a yield of over 82% of FAME is still achieved in the presence of 0.2% of water. The optimized reaction conditions, such as the molar ratio of DMC to methanol, the catalyst dosage and the reaction time, were investigated to produce high-quality biodiesel. The fuel properties determined and discussed in light of EN 14214 (European standards) demonstrate that the biodiesel produced using this new method has good flow properties with a cloud filter plugging point of –10 °C and a pour point of –9.4 °C. Furthermore, the amount of free glycerol was found to be as low as 0.018% in the biodiesel obtained directly from this new method without any further processing. The results of this study indicate the feasibility of producing quality biodiesel fuels without glycerol by coupling transesterifications.     

多频超声反应槽连续强化酸化油酯交换制备生物柴油研究

以平均酸值高达33.07 mgKOH/g不可食用的廉价酸化油为原料,利用自行设计的多频超声溢流槽连续强化酯交换反应生物柴油生产装置,先后经预酯化、酯交换两步反应,高效、低耗的制备生物柴油。主要考察了室温下物料流量(停留时间)、超声功率、超声频率及组合、KOH用量、醇油物质的量比对酯交换反应的影响及单位产品能耗。结果表明,多频组合超声辐射比单频更有利于生物柴油的制备;预酯化后的油料在流量为25 L/h(物料停留时间为54 min),催化剂(KOH)用量为1.2%(质量分数),醇油物质的量比为6∶1和各反应槽功率为200 W的条件下,甲酯产率达96.83%。50 L废弃酸化油能制得符合国标GB19147—2009的生物柴油48L,整个生物柴油制备过程总耗时和总耗电量仅为8.667 h、5.42 kWh。     

双环戊二烯苯酚树脂的合成新工艺

以双环戊二烯（DCPD）和苯酚为原料,甲磺酸为催化剂,合成了双环戊二烯苯酚树脂。适宜工艺条件:苯酚与DCPD摩尔比为5、反应温度120 ℃、反应时间5 h、催化剂质量分数为1.5%,收率89%。所得的双环戊二烯苯酚树脂（DPR）经催化加氢法在H2气压力1.5 MPa、催化剂Pd/Al2O3用量为原料质量分数的0.5%、反应温度80 ℃条件下对树脂进行脱色处理。 得到浅黄色双环戊二烯苯酚树脂,收率89%,经IR和1H NMR表征分析其为目的产物,产物指标达到国际同类产品的质量标准。     

The use of impregnated perlite as a heterogeneous catalyst for biodiesel production from marula oil

In this study, biodiesel was produced from marula (Sclerocarya birrea) oil using impregnated perlite with potassium hydroxide (KOH) as a heterogeneous catalyst. The effect of experimental variables such as temperature (°C), reaction time (h), methanol to oil ratio (mass %), and catalyst to oil ratio (mass %) on the transesterification process were investigated. Using a central composite design (CCD), a mathematical model was developed to correlate the experimental variables with the percentage yield of biodiesel. The model showed that optimum conditions for biodiesel production were as follows: catalyst to oil ratio of 4.7 mass %, temperature of 70.4°C, methanol to oil ratio of 29.9 mass %, and reaction time of 3.6 h. The yield of 91.4 mass % of biodiesel was obtained. It was also possible to recycle and reuse the modified perlite up to three times without any significant change in its catalytic activity. The X-ray diffraction (XRD) and the Brunauer-Emmett-Teller (BET) surface area showed no modifications in the perlite structure. The results show that the important fuel properties of marula biodiesel meet the American Society for Testing and Materials (ASTM) biodiesel standard properties.     

Transesterification of Soybean Oil Catalyzed by Calcium Hydroxide which Obtained from Hydrolysis Reaction of Calcium Carbide

Calcium carbide residue (CCR) was investigated in transesterification reaction of triglycerides to determine its viability as a solid catalyst for biodiesel synthesis. Literature survey showed that CCR has never been studied as a solid catalyst in the transesterification of triglyceride. The scope of the study includes the effects of CCR calcination temperature, calcination time, the alcohol/oil molar ratio, the catalyst amount (wt % of oil) and the reaction time. The relationship between chemical composition and catalytic activity of waste cement was also investigated. These CCR catalysts, thermally activated at 600 °C, can give rise to fatty acid methyl esters (FAME) purity higher than 99.5%, after 3 h of reaction, when oil/methanol molar ratio of 1/12 and 1 wt % of the catalyst were employed. Application of CCR as catalyst for biodiesel production in this study may not only provide a cost‐effective and environment friendly way of recycling CCR waste but also reduce hopefully the cost of biodiesel production.     

棉籽现场碱催化转酯化联产生物柴油和无毒棉粕

通过棉籽现场碱催化转酯化联产生物柴油和无毒棉粕,考察了棉仁中水的质量分数、粒径对产物中脂肪酸甲酯（FAME）的质量分数和棉粕中游离棉酚（FG）质量分数的影响;对反应过程中的醇油摩尔比、反应时间、催化剂用量、反应温度进行了单因素和正交实验考察。实验得到的反应适宜条件为,棉仁含水量在1.92%左右,棉仁粒径小于0.335mm,反应醇油摩尔比135∶1,反应3h,甲醇中氢氧化钠浓度0.10mol/L,反应温度30℃。在上述反应条件下,反应产物中甲酯的质量分数可达97%,棉粕中游离棉酚的质量分数为0.031%,低于FAO规定的国际标准。     

Biodiesel production and comparison using commercial lipase and chemical catalyst from Cassia auriculata oil

In this present investigation, Cassia auriculata was explored as a feedstock for production of biodiesel. Transesterification reaction was performed by both enzyme (lipase) and chemical (potassium hydroxide) catalyst with diverse acyl acceptors such as methanol, ethanol, propanol, n-propanol, butanol, n- butanol, and finally their biodiesel yield were also recorded. Process optimization was performed by both one factor at a time method and response surface method. The maximal biodiesel yield of 92% (weight/weight) was obtained at the following optimal conditions: Oil:Methanol molar ratio of 1:6 (moles/moles), the lipase concentration of 2% (weight/weight), at 35 ?°C and 120 ?min. The highest biodiesel yield from Cassia auriculata oil was occurred with excess methanol that aids the equilibrium shift in the forward direction. The kinetics of the transesterification reaction was investigated under optimal conditions and the activation energy was found to be 14.91 ?kJ/mol. Simultaneously Gas Chromatography – Mass Spectroscopy was also carried out for the biodiesel produced from Cassia auriculata and the same has been reported. The GC analysis declares the existence of fatty acid esters like hexadecanoic acid methyl ester, methyl stearate and the peak with retention time 12.8 ?min signifies the evidence of hexadecanoic acid methyl ester with 28% of yield content. This investigation also evaluated the biodiesel quality produced from lipase-transesterified Cassia auriculata oil based on fuel properties. Biodiesel properties Flash Point (FC), Pour Point (PP) and kinematic viscosity were compared with American (ASTM 6751) and European (EN 14214) Standards. Cassia auriculata oil had PP 6.7 ?°C and Kinematic viscosity (813 ?kg/m³) that agreed with both the standards. Thus this study showed that Cassia auriculata oil could be a better fuel alternative with further improvement of fuel properties.     

CuCl2掺杂聚苯胺催化合成苯甲醛1,2-丙二醇缩醛

缩醛是一类重要化合物,具有原料来源丰富、生产工艺简单、化学性质稳定等优点,近20年来作为新型香料在日用香精和食品香精中均有广泛应用[1-2]。根据酸催化机理,Lewis酸可增强羰基碳的正电性,有利亲核试剂的进攻。研究表明,不少无机盐都是这类反应的高效、高选择性的催化剂,又因为无机盐价廉、易得等优点,所以用其作为催化剂具有更加重要的实际意义。聚苯胺(PAn)以其独特的掺杂现象及良好的稳定性为催化载体的选择提供了新的途径[3-4]。若以PAn为载体,将具有催化活性的路易斯酸掺杂其中,可降低路易斯酸的流失量,并克服其易潮解、腐蚀设备…     

固载杂多酸SiW_(12)/C催化合成富马酸二甲酯

用自制的固体杂多酸催化剂SiW12 /C进行催化酯化合成富马酸二甲酯 (DMF) .探讨了催化剂用量、醇 /酸比、反应时间、反应温度等动力学条件对合成DMF的影响 .确定了合成DMF的最佳合成工艺条件 :醇 /酸物质的量比为 6∶1,催化剂用量为富马酸质量的 2 .5 % ,反应时间 7.0h ,反应温度为回流温度 ,酯化率可达 90 .6 % .结果表明 ,该催化剂催化活性高 ,可重复使用 ,后处理容易 ,生产成本低且无三废污染 .