Reaction Kinetics of Soybean Oil Transesterification Using Heterogeneous Metal Oxide Catalysts

Homogeneous acid or base catalysts dissolve fully in the glycerol layer and partially in the fatty acid methyl ester (biodiesel) layer in the triglyceride transesterification process. Heterogeneous (solid) catalysts, on the other hand, can prevent catalyst contamination making product separation much simpler. In the present work, the transesterification kinetics of five different solid catalysts with soybean oil is presented. It is found that heterogeneous catalysts require much higher temperatures and pressures to achieve acceptable conversion levels compared to homogeneous catalysts. Subsequent to preliminary investigations, transesterifications were conducted for selected high performance solid catalysts, i.e., MgO, CaO, BaO, PbO, and MnO₂ in a high pressure reactor up to a temperature of 215 °C. The yield of the fatty acid methyl esters and the kinetics (rate constant and order) of the reaction are estimated and are compared for each catalyst.     

Transesterification Kinetics of Soybean Oil for Production of Biodiesel in Supercritical Methanol

A kinetic study on soybean oil transesterification without a catalyst in subcritical and supercritical methanol was made at pressures between 8.7 and 36 MPa. It was found that the conversion of soybean oil into the corresponding methyl esters was enhanced considerably in the supercritical methanol. The apparent activation energies of the transesterification are different with the subcritical and the supercritical states of methanol, which are 11.2 and 56.0 kJ/mol (molar ratio of methanol to oil: 42, pressure: 28 MPa), respectively. The reaction pressure considerably influenced the yield of fatty acid methyl esters (FAME) in the pressure range from ambient pressure up to 25 MPa (280 °C, 42:1). The reaction activation volume of transesterification in supercritical methanol is approximately −206 cm³/mol. The PΔV ^≠ term accounts for nearly 10% of the apparent activation energy, and can not be ignored (280 °C, 42:1).     

Transesterification of edible and non-edible oils over basic solid Mg/Zr catalysts

A series of Mg–Zr catalysts with varying Mg to Zr ratios was prepared by co-precipitation method. These catalysts were characterized by BET surface area, X-ray diffraction, X-ray photo electron spectroscopy and temperature programmed desorption of CO₂. The catalytic activity of these catalysts was evaluated for the room temperature transesterification of both edible and non-edible oils to their corresponding fatty acid methyl esters. The catalyst with Mg/Zr (2:1 wt./wt.%) exhibited exceptional activity towards transesterification reaction within short reaction time. The effects of different reaction parameters such as catalyst to oil mass ratio, reaction temperature, reaction time and methanol to oil molar ratio were studied to optimize the reaction conditions. The reasons for the observed activity of these catalysts are discussed in terms of their basicity and other physico-chemical properties.     

High-Area Ti/Pt Electrodes for the Electrochemically Catalyzed Transesterification of Soybean Oil with Methanol

Biodiesel fuel is a renewable energy source normally produced in industry by using an alkaline homogeneous catalyst to promote the transesterification of oil and methanol to fatty acid methyl ester (FAME). Undesirable side reactions occur when poorly refined oils are used, leading to serious problems of product separation and low FAME yield. Therefore, about 85% of the cost of biodiesel is determined by the cost of the feedstock. Here, we describe the development of high-area Pt films deposited on Ti substrates for the electrolytic synthesis of biodiesel from soybean oil containing water, without the addition of catalyst. The higher both the calcination temperature and the number of layers deposited on the Ti surface, the higher the electrochemically active area of Pt exposed to surface. Conversion into esters in electrolysis is proportional to the increase in the superficial area of the Ti/Pt electrodes. Thus, it is possible to synthesize biodiesel using electrodes containing very low amounts of Pt (<0.441 mg cm^?2), an important parameter in the industrial production of biodiesel.     

Feasibility of Palm Oil as the Feedstock for Biodiesel Production via Heterogeneous Transesterification

The production of biodiesel has become popular recently as a result of increasing demand for a clean, safe and renewable energy. Biodiesel is made from natural renewable sources such as vegetable oils and animal fats. The conventional method of producing biodiesel is by reacting vegetable oil with alcohol in the presence of a homogenous catalyst (NaOH). However, this conventional method has some limitations such as the formation of soap, usage of significant quantities of wash water and complicated separation processes. Heterogeneous processes using solid catalysts have significant advantages over homogenous methods. Currently, more than 90 % of world biodiesel is produced using rapeseed oil. The production of biodiesel from rapeseed oil is considered uneconomical, considering the fact that palm oil is currently the world's cheapest vegetable oil. Therefore, the focus of this study is to show the feasibility of producing biodiesel from palm oil using montmorillonite KSF as a heterogeneous catalyst. The heterogeneous transesterification process was studied using design of experiment (DOE), specifically response surface methodology (RSM) based on a four‐variable central composite design (CCD) with α = 2. The transesterification process variables were reaction temperature, x₁ (50–190 °C), reaction period, x₂ (60–300 min), methanol/oil ratio, x₃ (4–12 mol mol^–1) and the amount of catalyst, x₄ (1–5 wt %). It was found that the conversion of palm oil to biodiesel can reach up to 78.7 % using the following reaction conditions: reaction temperature of 155 °C, reaction period of 120 min, ratio of methanol/oil at 10:1 mol mol^–1 and amount of catalyst at 4 wt %. From this study, it was shown that montmorillonite KSF catalyst can be used as a solid catalyst for biodiesel production from palm oil.     

Biolubricant Production of 2‐Ethylhexyl Palmitate by Transesterification Over Unsupported Potassium Carbonate

Owing to the decrease of global oil price, development of downstream value‐added products is important to biodiesel industry. In this study, we used palmitic acid methyl ester (PAME) as a starting material to produce 2‐ethylhexyl palmitate (2‐EHP), an environmentally friendly biolubricant product, which was derived from the transesterification of fatty acid methyl esters and long chain fatty alcohols. Conventional synthetic routes of 2‐EHP have disadvantages, including high catalyst price, low conversion efficiency, and pollution issues. To solve these problems, in situ transesterification of PAME with 2‐ethylhexanol (2‐EH) was conducted over unsupported potassium carbonate as heterogeneous catalyst. The optimal reaction temperature, 2‐EH to PAME molar ratio, and catalyst to PAME mass ratio were 180 °C, 3:1, and 3.0 wt%, respectively. The PAME conversion reached up to 100% within 1 hour under the optimal conditions. In addition, a kinetic model describing the experimental data over a temperature range of 160–180 °C was developed. The dependence of kinetic rate constant (k) on temperature was evaluated, and the activation energy (E_a) for the transesterification of PAME with 2‐EH was calculated to be 57.04 kJ mol^?1.     

Heterogeneous Catalyst of Mixed K Compounds/Ca‐Al‐Graphite Oxide for the Transesterification of Soybean Oil to Biodiesel

A novel heterogeneous solid base catalyst was prepared by loading of Ca‐Al‐graphite oxide with mixed potassium salts and applied in the transesterification of soybean oil with methanol to produce biodiesel. The catalysts were characterized by Hammett indicators, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X‐ray spectrometry, and transmission electron microscopy. The effects of the methanol‐to‐oil molar ratio, catalyst amount, reaction temperature, stirring rate, and reaction time were investigated to optimize the transesterification reaction conditions. Moreover, the prepared catalyst retains its activity after being used for four cycles. In particular, the solid base catalyst can be effectively and easily separated from the reaction system, which may provide significant benefits for the development of an environmentally benign and continuous process for preparing biodiesel.     

K_2O/CaO-SBA-15催化大豆油制备生物柴油研究

通过浸渍法制备固体碱催化剂:K2O-SBA-15、CaO-SBA-15和K2O/CaO-SBA-15,用于催化大豆油和无水甲醇发生酯交换反应制备生物柴油,并进行X射线衍射(XRD),氮气吸附脱附表征。结果表明,负载固体碱后,没有改变介孔分子筛SBA-15的规则孔道结构,并且碱金属氧化物均匀负载在SBA-15的孔壁上。按三组分四因素的正交试验设计方案进行实验,表明各因素影响制备生物柴油的程度依次为:反应时间反应温度醇油摩尔比催化剂用量。反应的最佳条件为:以3%K2O/3%CaO-SBA-15为催化剂,反应温度60℃,反应时间3h,醇油摩尔比为16:1,催化剂用量为油重的3%,可得生物柴油产率为87.12%。     

Kinetic Modeling of Sunflower Oil Methanolysis Catalyzed by Calcium‐Based Catalysts

The kinetic model originally developed for quicklime‐catalyzed methanolysis of sunflower oil was tested for another three calcium‐based catalysts, namely, neat CaO, Ca(OH)₂, and CaO·ZnO. This model includes the changing reaction mechanism and the triacylglycerol (TAG) mass transfer. The applicability and generalization capability of this model for heterogeneous methanolysis reaction catalyzed by calcium‐based catalysts was evaluated. As indicated by the high coefficient of determination and the relatively small mean relative percentage deviation, the model was a reliable predictor of the time variation of TAG conversion degree in the sunflower oil methanolysis over all four calcium‐based catalysts within the ranges of the reaction conditions applied. This model is recommended in general for describing the kinetics of sunflower oil methanolysis over calcium‐based catalysts.     

Biodiesel Production from Rubber Seed Oil by Transesterification Using a Co‐solvent of Fatty Acid Methyl Esters

Rubber seed oil (RSO) is a high‐potential feedstock for the production of biodiesel fuel (BDF) in Asia. Transesterification using fatty acid methyl esters (FAMEs) as co‐solvents was developed for BDF production from RSO with high content of free fatty acids (FFAs). The homogeneous system (FAMEs/triglyceride/methanol) was attained when the FAME content was more than 30 wt %. After esterification of RSO, the crude RSO obtained was transesterified with FAMEs as a co‐solvent. The quality of BDF with high FAME content satisfied the criteria of the EN 14214/JIS K2390 standards. These results suggest that FAMEs converted from FFAs can be applied as a co‐solvent and, thus, reused for BDF production.     

Kinetics of Multi‐Step Redox Processes by Time‐Resolved In Situ X‐ray Diffraction

The kinetics of redox reactions of iron oxide in oxygen carrier 50Fe₂O₃/MgAl₂O₄ are examined using different time‐resolved techniques. Reduction kinetics are studied by H₂ temperature‐programmed reduction (H₂‐TPR) monitored by time‐resolved in situ XRD. In contrast to conventional TPR, in situ XRD distinguishes the three‐stage reduction of Fe₂O₃ → Fe₃O₄ → FeO → Fe. It also shows that the oxidation of Fe → Fe₃O₄ by CO₂ has no intermediate crystalline phases, explaining why its kinetics can easily be investigated by conventional CO₂ temperature‐programmed oxidation (CO₂‐TPO). A shrinking core model which takes into account solid state diffusion allows describing the experimental data.     

Transesterification of triglycerides with methanol over thermally treated Zn5(OH)8(NO3)2×2H2O salt

Methanolysis of natural oil, i.e. castor oil and triacetin, a model compound for the transesterification of triglycerides in biodiesel production was studied under atmospheric pressure at temperature of 50-60 °C. As-received zinc hydroxy nitrate Zn₅(OH)₈(NO₃)₂×2H₂O (Zn-5) and samples obtained by thermal treatment of Zn-5 for 2 h in the temperature range of 105-300 °C were used as the catalysts. The catalysts were characterized by thermogravimetric (TG) analysis, X-ray powder diffraction (XRD), infrared spectroscopy (FTIR), nitrogen sorption (BET) and scanning electron microscopy (SEM). The effect of thermal treatment of Zn-5 salt on the activity and reusability in methanolysis of triglycerides was studied. During thermal treatment of as-received Zn-5 salt a gradual decomposition via various hydroxy nitrates intermediates such as Zn₅(OH)₈(NO₃)₂ and Zn₃(OH)₄(NO₃)₂ to ZnO occurred. This was accompanied by significant morphological and textural changes. Plate-like particles of Zn-5 salt reorganized into spherically shaped particles of ZnO. Moreover, decrease in specific surface area and porosity occurred. In methanolysis of both triglycerides, the activity of Zn-catalysts gradually decreased as the temperature of thermal treatment increased and the activity of ZnO, a final product of thermal decomposition was very low. The most active was as-received Zn-5 salt and its morphological/chemical properties did not change during methanolysis reaction performed at temperature of 50-60 °C. Moreover, the activity of original Zn-5 salt was fully restored after methanol/THF washing of spent catalysts. The activity of as-received Zn-5 catalyst was preserved under successive use in catalytic tests. The activity of thermally treated Zn-5 salt (at 140 °C) did not restore after methanol/THF washing and during subsequent use of Zn-5-140 catalyst its activity successively decreased.     

Optimization of Process Variables for Biodiesel Production Using the Nanomagnetic Catalyst CaO/NaY‐Fe3O4

Due to decreasing oil resources, alternative fuels such as biodiesel are required. The nanomagnetic catalyst CaO/NaY‐Fe₃O₄ was synthesized and used for biodiesel production from canola oil. The structure of the catalysts was characterized by X‐ray diffraction, field emission scanning electron microscopy, Brunauer‐Emmett‐Teller method, Fourier transform infrared spectroscopy, and vibrating sample magnetometer method. To optimize the influence of the operating variables, such as the methanol/canola oil molar ratio, the amount of catalyst, and the reaction time, on the yield of transesterification reaction, an experimental design was applied based on the Box‐Behnken method. The optimum values of these variables were predicted by the cubic model and were in excellent agreement with the experimental results.     

Biodiesel Production Using a Carbon Solid Acid Catalyst Derived from β‐Cyclodextrin

A novel carbon solid acid catalyst was prepared by incomplete hydrothermal carbonization of β‐cyclodextrin into small polycyclic aromatic carbon sheets, followed by the introduction of –SO₃H groups via sulfonation with sulfuric acid. The physical and chemical properties of the catalyst were characterized in detail. The catalyst simultaneously catalyzed esterification and transesterification reactions to produce biodiesel from high free fatty acid (FFA) containing oils (55.2 %). For the as‐prepared catalyst, 90.82 % of the oleic acid was esterified after 8 h, while the total transesterification yield of high FFA containing oils reached 79.98 % after 12 h. By contrast, the obtained catalyst showed comparable activity to biomass (such as sugar, starch, etc.)‐based carbon solid acid catalyst while Amberlyst‐15 resulted in significantly lower levels of conversion, demonstrating its relatively high catalytic activity for simultaneous esterification and transesterification. Moreover, as the catalyst can be regenerated, it has the potential for use in biodiesel production from oils with a high FFA content.     

Biodiesel Synthesis from Styrax confusus Hemsl Catalyzed by S2O82−/ZrO2‐TiO2‐Fe3O4

Biodiesel has been identified as a suitable resource that can be produced from biomass such as Styrax confusus Hemsl. In the current study, biodiesel was synthesized from Styrax confusus Hemsl oil catalyzed by a magnetic solid acid heterogeneous catalyst S₂O₈^2?/ZrO₂‐TiO₂‐Fe₃O₄, which had a high recovery rate and reusability. The catalyst was prepared by co‐precipitation and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction and Brunauer, Emmett and Teller (BET) adsorption. The properties of the catalyst, including the recovery rate, usage count, magnetic susceptibility and catalytic efficiency, were studied. The results showed that the catalyst has a BET pore diameter of 1.74 nm, BET area of 7.3 m²/g, molar magnetic susceptibility of 1.83 × 10^?5 m³/kg and tetragonal structure. In addition, the influences of reaction conditions on yields of biodiesel were also discussed. A fatty acid methyl ester (FAME) yield of 90.02 % was obtained under the conditions of reaction time 1.5 h, reaction temperature 373 K, catalyst amount 5 %, and methanol‐to‐oil molar ratio 8:1. A FAME yield of 65.5 % was obtained when the catalyst was used for the fourth time.     

Comparison of soybean oil and castor oil methanolysis in the presence of tin(IV) complexes

In this paper we present and discuss the results obtained from the methanolysis of two vegetable oils with very distinct triglyceride composition, castor oil and soybean oil, using Lewis acid Sn(IV)-based compounds as catalysts. For all transesterification reactions, two different types of reactors were employed; an open glass (OG) reactor equipped with a reflux condenser, and a closed steel (CS) reactor. The results indicated that in all reactions assayed, regardless of the Sn(IV)-based catalyst employed, the yields obtained with the methanolysis of castor oil are generally lower than those carried out with soybean oil. Furthermore, independently of the oil used, the reaction yields tend to be higher when the CS reactor was employed.     

二氧化硅-磺酸固体酸催化大豆油与异丙醇的酯交换反应

通过溶胶-凝胶法制备了二氧化硅-磺酸(SiO2-SO3H)固体酸催化剂,并用于大豆油与异丙醇的酯交换反应制备生物柴油,考察了催化剂的处理温度、异丙醇与大豆油的摩尔比、催化剂用量、正庚烷用量和反应时间对酯交换反应的影响。结果表明,二氧化硅-磺酸(SiO2-SO3H)具有较高的酯交换反应催化活性。确定制备生物柴油的最佳条件如下:催化剂处理温度为120℃、醇油摩尔比为6∶1、催化剂用量(以大豆油质量计)为5.0%、正庚烷用量(以大豆油质量计)为30.0%、反应时间为6.0h。在该条件下,大豆油异丙酯产率可达96.12%。     

Kinetics of Heterogeneous Deacetylation of β‐Chitin

β‐Chitin was extracted from squid pens and its heterogeneous alkaline deacetylation was performed under various conditions. The kinetics of the first, second and third deacetylation reaction of β‐chitin was investigated under conditions minimizing bulk mass transfer. It was found that the effects of temperature and reaction time on the first, second and third deacetylation of β‐chitin were similar. A shrinking core model of a sphere with surface reaction is proposed to describe the deacetylation reaction of β‐chitin. The experimental data fit the theoretical model very well. The controlling step of the reaction changes from the chemical reaction to diffusion through an ash layer with increase in temperature and time of deacetylation. The phenomenon of stagnation is mainly caused by the structure of β‐chitin.     

Biodiesel (FAME) Productivity,Catalytic Efficiency and Thermal Stability of Lipozyme TL IM for Crude Palm Oil Transesterification with Methanol

Crude palm oil (CPO) transesterification with methanol at room temperature is an important factor for optimizing biodiesel processing costs with respect to energy input; in addition, good stability of expensive lipase activity was ensured and is reported in this study. The enzyme loading, agitation speed and reaction time at a constant operating temperature of 30 °C were studied to find favourable operational conditions using a factorial design. Statistical analysis was used to assist the enzymatic transesterification so that a reduced mass transfer effect was achieved to obtain high FAME yields. The combination of optimum enzyme loading of 6.67 wt% and 150 rpm agitation speed for the system at 30 °C gave 81.73% FAME yield at 4 h and a production rate of 85.86% FAME yield/h. The high viscosity of CPO observed at 30 °C compared to 40 °C hindered the achievement of 96.15% FAME yield at room temperature. It was found that an increase of 10 °C invariably deactivated the lipase, but was compensated by the enhanced FAME production rate with 96.15% FAME yield after only 4 h reaction time. Thus, 40 °C was considered the most suitable operating temperature for lipozyme TL IM to catalyze CPO transesterification.     

Structure and morphology of poly(β‐hydroxybutyrate) synthesized by ring‐opening polymerization of racemic (R,S)‐β‐butyrolactone with distannoxane derivatives

Predominantly syndiotactic poly((R,S)‐β‐hydroxybutyrate) (PHB) was synthesized by ring‐opening polymerization of racemic β‐butyrolactone with distannoxane derivatives as catalysts. We have studied the polymerization of (R,S)‐β‐BL using distannoxane derivatives as catalysts and the effects of polymerization time on crude yield and molecular weight of the polymers obtained. Then, a more detailed study of the characterization of polymers obtained using hydroxy‐ and ethoxy‐distannoxanes was performed. ¹³C NMR spectroscopy resolved stereosequences in synthetic PHB at the diad level for the carbonyl carbon and at the triad level for the methylene carbon. These analyses show that distannoxane catalysts produce preferentially syndiotactic polyesters (syndiotactic diads fraction from 0.56 to 0.61). Triad stereosequence distribution of PHB samples agrees favourably with the Bernoullian statistical model of chain‐end control, where ideally Φ = 4(mm) (rr)/(mr + rm)² = 1 for perfect chain‐end control. Polymer samples synthesized from distannoxane catalysts are composed of two distinct transition endotherm components with peak temperatures of approximately 42 °C and 75 °C. The formation of two melting endotherms may be due to the presence of two different crystalline structures. © 2000 Society of Chemical Industry