Catalyzed Transesterification Reaction Research Articles

Simplified Rate Expression for Palm Kernel Oil (PKO) and Methanol Alkali Catalyzed Transesterification Reaction

The need for the development of simplified kinetics rates expression (-RA) for Vegetable Oils Alkali catalyzed Transesterification processes to enhance biodiesel production motivated this study. The study, therefore aimed at proposing unified simple rate expression that may be a useful prelude to design various reactor types for Alkali Catalyzed Transesterification of palm kernel oil (PKO) and Methanol reactions. The kinetics rate expression is proposed using simple explicit algebraic technique with the consideration that alkali catalyzed transesterification reaction of palm kernel oil and methanol is a reversible bimolecular reaction. The proposed kinetic reaction rate expression is developed as a function of conversion (XA), reactants and products concentration and reaction rate constants (k1 and k2). The kinetics reaction rate expression obtained is further evaluated on the basis of reactants and product molar masses and densities. The developed models were simulated using Matlab codes programming techniques. The results for kinetic reaction rates (-RA & -ReA) decreases with decrease in fractional volume change (e) and increase in fractional conversion at constant reaction time. The results were quite compatible with those of inferential laboratory physicochemical characterization reported.

Simplified Rate Expression for Palm Kernel Oil (PKO) and Methanol Alkali Catalyzed Transesterification Reaction

The need for the development of simplified kinetics rates expression (-RA) for Vegetable Oils Alkali catalyzed Transesterification processes to enhance biodiesel production motivated this study. The study, therefore aimed at proposing unified simple rate expression that may be a useful prelude to design various reactor types for Alkali Catalyzed Transesterification of palm kernel oil (PKO) and Methanol reactions. The kinetics rate expression is proposed using simple explicit algebraic technique with the consideration that alkali catalyzed transesterification reaction of palm kernel oil and methanol is a reversible bimolecular reaction. The proposed kinetic reaction rate expression is developed as a function of conversion (XA), reactants and products concentration and reaction rate constants (k1 and k2). The kinetics reaction rate expression obtained is further evaluated on the basis of reactants and product molar masses and densities. The developed models were simulated using Matlab codes programming techniques. The results for kinetic reaction rates (-RA & -ReA) decreases with decrease in fractional volume change (e) and increase in fractional conversion at constant reaction time. The results were quite compatible with those of inferential laboratory physicochemical characterization reported.

Contemporary approaches towards augmentation of distinctive heterogeneous catalyst for sustainable biodiesel production

Abstract In recent times, demand for energy has significantly increased due to the depletion of fossil fuels and the fast-industrial revolution. This has created a wide space for the development of sustainable and renewable energy sources. Biodiesel has attained exceptional contemplation among other biofuels due to the use of renewable and low-cost resources. Selection of suitable catalyst plays a vital role in biodiesel production by a catalytic transesterification reaction. Compared to homogeneous catalysts, heterogeneous catalysts are most preferred as they have high selectivity and stability with increased biodiesel yield. Heterogeneous catalyst has made incredible development in biodiesel production under mild operating conditions and has less impact on the environment. Nanocatalysts are the effective heterogeneous catalyst, which has brought a tremendous revolution in biodiesel production in recent years. Thus, present review provides a comprehensive analysis of the use of heterogeneous catalyst, importance and challenges associated in biodiesel production.

Choline derivatives immobilized on silica to catalyze transesterification reaction for production of glycerophosphocholine.

Choline derivatives were covalently immobilized on the surface of γ -aminated silica. The obtained immobilized choline derivative was then successfully used for a transesterification reaction to produce glycerophosphocholine (GPC). Fourier transform infrared analysis and thermogravimetric analysis/differential thermal gravimetry indicated that the surface of the γ -aminated silica was covered by choline derivatives and the highest immobilization amount reached 1.1 mmol/g under optimal conditions. More importantly, the highest yield of GPC reached 97.9% during transesterification. With regard to GPC in food or medicine for human use, the immobilization technology can avoid catalyst contamination of the product and increase the safety of the product. The recyclability and stability of the immobilized choline derivative were excellent, as demonstrated by its use 20 times without any loss of productivity. A first-order kinetic model was employed and the relevant parameters were calculated to investigate kinetic characteristics of transesterification.

Transesterification of Palm Oils Catalyzed by Ionic Liquid in Microwave Heated Reactors

Biodiesel is a renewable, carbon neutral liquid fuel produced from vegetable oils or animal fats with alcohol via catalytic transesterification reaction. Conventionally, alkaline-catalysed transesterification using convective heating takes long time to complete. Alkaline catalysts used are usually non-recyclable, environmentally unfriendly and could react with free fatty acids to form soap. Recently, ionic liquids have been shown to be effective in catalyzing transesterification. Furthermore, microwave irradiation has been shown to boost heat transfer to the reactants, making the reaction time shorter than the conventional heating. In this work, biodiesel production from microwave-irradiated transesterification of palm oils with methanol using a green ionic liquid was investigated. The ionic liquid (ChOH) was synthesized from choline chloride (ChCl) with potassium hydroxide (KOH) and characterized by Fourier transform infrared spectroscopy. The batch experiments were setup and carried out in an 800 W microwave oven with a flask reactor connected to a condenser. The continuous experiments were setup and carried out with a polytetrafluoroethylene (Teflon) tubing connected to a Teflon valve and a pump. Operating condition was oil to methanol ratio (1:15), reaction time (8 min), power of microwave (800 W), and catalyst loading (4 wt%). Methyl ester content was determined by gas chromatography and mass spectrometer. From the findings, it was shown that the ionic liquid was effective in catalysing transesterification of palm oils. Microwave heating proved to accelerate the reaction in short time. The methyl ester content was found to be 87 and 82 % for the batch and continuous experiments. The ester content was quite low, compared to the conventional heating. Further investigation was needed to find high biodiesel yield. The ChOH could also be reused several times but its effectiveness to produce biodiesel may be degraded, in comparison with the fresh catalyst.

Renewable sources: applications in personal care formulations.

A global tendency for products considered environmentally sustainable, and ecologically obtained led the industry related to personal care formulations to fund the research and the development of personal care/cosmetics containing ingredients from natural resources. Furthermore, consumers are aware of environmental and sustainability issueans, thus not harming the environment represents a key consideration when developing a new cosmetic ingredient. In this study we review some examples of active ingredients or raw materials used in cosmetics/personal care/biomedical products that are coming from either through biotechnological systems, or as byproducts of several industries. A skin formulation containing biosynthetic actives, prepared by us and the study regarding its dermocosmetic properties are also described. The need for the standardization processes, the safety assessment tools, the improvement of the exploitation methods of these renewable sources in order the production to be ecologically and economically better are also discussed.

Effect of Light Intensity on Algal Growth in Designed Hybrid Photobioreactor and Biodiesel Production

In current scenario algal fuel is considered as the most viable solution for the depleting non-renewable fuel sources. This study demonstrates the controlled, continuous production of the microalgae species Chlorella Pyrenoidosa in a novel designed hybrid photobioreactor aimed to the later production of biodiesel. The reactor is operated at different light intensity and its effect on the biomass production and pH was assessed. The final biomass is harvested by centrifugation preceded by sedimentation from which the algal lipids are extracted using solvent extraction method and biodiesel by acid catalysed transesterification reaction is produced. The species population density is found to be exponential at 7130 LUX at a photoperiod of 8/16(L/D). The biomass growth in the developed design is established as a factor of 2.88 with respect to optical density. At the light intensity of 7130LUX, the developed Hybrid Photobioreactor yields a dry algal mass of 2.09g/L with a lipid productivity of 1.01gL-1day-1 and 70.62% of fatty acid methyl esters (FAME). The analysis of FAME is done using gas chromatography and a maximum of 73.4% biodiesel composition is observed.

Synthesis and characterization of Argania spinosa (Argan oil) biodiesel by sodium hydroxide catalyzed transesterification reaction as alternative for petro-diesel in direct injection, compression ignition engines

In this research work, the optimization conditions for obtaining optimum biodiesel yield from argan oil as well as the quantification of degree of interactions between reactants and biodiesel yield were investigated by using a response optimization model and response surface methodology (RSM) respectively. Similarly, a regression polynomial model was used to develop a unified equation for predicting the expected yield of Argan biodiesel for different values of reactant variables and a regression coefficient of 92.56% was obtained.The Argan oil was extracted from its kernel by using a soxhlet extractor with hexane as extraction solvent and 54.50% oil yield was obtained. The fatty acid compositional analysis was done by using a Shimadzu GCMS QP2010 SE Gas-chromatograph-mass spectrometer.The spectrometer analysis shows that the oil has 80.90% of unsaturated fatty acid with oleic and linoleic acid constituting larger percentages respectively. A sodium hydroxide catalyzed transesterification reaction was used to convert the triglyceride in the oil to fatty acid methyl ester under standard conditions and the fuel properties of the oil and its ester were measured by using the American society for testing and materials (ASTM) procedures. A Fourier transform infrared spectroscopic (FTIR) technique was used for qualitative characterization of biodiesel functional groups in order to affirm the complete conversion of the oil into biodiesel.Results showed that the cold flow behaviour in terms of cloud point, pour point, cold filter plugging point (CFPP) and Low temperature flow test (LTFT) and critical properties such as cetane number, calorific value, iodine value, density, flash point, ash percentage and carbon residue of the Argan biodiesel showed a good agreement with ASTM D6751-07b and European committee for standardization (EN 14214) standard requirements. Hence, its application in compression ignition engines will pose no threat as far as performance, combustion and emission qualities are concerned. Finally, the Argan biodiesel has a very high higher heating value (HHV) of 40,665 kJ/kg which is very uncommon of other vegetable oils methyl esters and thus facilitate better heat release during combustion and improves engine performance.

Reactive Compatibilization of Poly(lactic acid) and Polycarbonate Blends Through Catalytic Transesterification Reactions

The combination of poly(lactic acid) (PLA) with polycarbonate (PC) which presents high inherent thermal stability and mechanical properties is an attractive strategy to overcome PLA brittleness and poor thermal resistance. To improve affinity between the two materials and their dispersion into the blend, an organophilic montmorillonite (MMT) has been added and reactive compatibilization through catalyzed transesterification has been investigated. The properties were studied using differential scanning calorimetry (DSC), thermogravimetry (TG), dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The study of the thermal properties revealed the immiscibility of the uncatalyzed blend but noticeable changes were detected on the PLA crystallization and melting behaviors after the addition of the catalyst. The SEM observations showed that MMT and the catalyst contribute in the improvement of the dispersion. The TG results revealed that MMT increases the thermal stability of the blend and showed new stages of decomposition due to the different structures resulting from the interchange reactions.

Kinetic modeling, mechanistic, and thermodynamic studies of HPW-MAS-9 catalysed transesterification reaction for biodiesel synthesis

The kinetics and reaction mechanism of methanolysis of unrefined green seed canola oil using heterogeneous HPW-MAS-9 composite catalyst have been investigated. The activity coefficients of the reactant and product species were estimated using the UNIQUAC method. Eley-Rideal reaction pathway with the surface reaction of adsorbed methanol as the rate controlling step, was found to be a reliable representation of the observed kinetics. Other kinetic models deduced from pseudo-homogenous (PH) and Langmuir-Hinshelwood-Hougen-Watson (LHHW) were rejected based on statistical analysis. Ea (activation energy), ∆H‡ (enthalpy of activation), ∆G‡ (free energy of reaction), and ∆S‡ (entropy of activation) for the reaction were found to be 72.5 kJ mol−1, 68.9 kJ mol−1, 58.3 kJ mol−1, and 0.04 kJ mol−1, respectively. The positive values of ∆H‡ and ∆G‡ indicated that the reaction is endothermic and non-spontaneous. Intricate mechanistic details for the stepwise transesterification reactions were deduced from the kinetic and thermodynamic parameters. On the basis of the ΔS‡, the reaction of triglyceride to diglyceride followed the dissociative pathway (SN 1 mechanism), whereas the reactions of diglyceride to monoglyceride and monoglyceride to glycerol proceeded via the associative pathway (SN 2 mechanism).

Isolation and characterization of methyl caprylate from virgin coconut oil (VCO)

Caprylic acid is a medium length fatty acid with many potential applications, from bioherbicides to dietary supplements. It was found as a minor constituent of coconut oil and palm kernel oil fatty acids. This study prepared isolated methyl caprylate from virgin coconut oil (VCO) using low pressured fractionated distillation and review its potency as a by-product of Lauric acids production. Neutralized VCO was esterified using basic catalyzed transesterification reaction producing methyl esters of mixed fatty acids. Low pressured fractionated distillation of methyl esters was performed using temperature of 80-120°C, 120-130°C, and 130-150°C. This process produced three fractions of distillates with a volume ratio of 21:19:1, respectively. Gas chromatography analysis using a flame ionization detector confirmed the first fraction of distillates as methyl caprylate.

Conversion of Pistacia atlantica mutica oil to trimethylolpropane fatty acid triester as a sustainable lubricant

Biolubricants have received growing interest as potential substitutes to conventional petroleum-based lubricants. Due to their renewability, biodegradability, and superior properties compared with mineral lubricants, they can play a significant role in overcoming some of the global challenges such as dependency on petroleum-based products, reduction in energy consumption, and environmental pollution. The objective of this research is to determine effective factors in biolubricant synthesis from Pistacia atlantica mutica oil as a novel indigenous feedstock which covers more than 1.2 million hectares of jungles in Iran. In this regard, a solid base–catalyzed transesterification reaction was applied in the presence of potassium carbonate as a cost-effective heterogeneous catalyst. The reaction parameters then were optimized using response surface methodology. The optimum values of operating parameters for the reaction were the methyl ester to trimethylolpropane molar ratio of 5:1, a vacuum pressure of 424.5 mmHg, and a catalyst concentration of 1.45 wt.% that resulted in the reaction yield of 82.5%. The physicochemical properties of the final product were evaluated and were comparable with those of the ISO VG-22 reference lubricant standard.

A new raw material in the production of biodiesel: purple pinion seeds.

Biodiesel is an alternative fuel that is produced through oil plants or animal fat. It is a renewable energy source, with biodegradable characteristics, to emit less pollutant than diesel. Thus, this work aims to show the production of biodiesel from the purple-pinion (Jatropha gossypiifolia L.) seeds. In addition to the synthesis, the physical-chemical characterization of both the raw material and the final product was carried out. The biodiesel synthetic route was performed by the basic catalytic transesterification reaction, using potassium hydroxide (KOH) in the presence of methanol (CH3OH) in the molar ratio of 1: 3 (oil: methanol). As a result, it was observed that the mass conversion of the biodiesel was 22.05 g. The physical-chemical analyzes carried out were acid index of 0.106 mgKOH / g, according to ANP technical resolution. The peroxide index of 1.03 meqO2 / kg, the kinematic viscosity of 20 ° C to 40 ° C, obtained was 6.455 mm2/s and 3.5343 mm2/s, the values are close to the ANP technique resolutions. Stability was 0.26 hours, and the biodiesel burning test was executed for approximately 3 hours. Therefore, there is a high viability of biodiesel production through the purple pinion seeds.

Optimized transesterification reaction for efficient biodiesel production using Indian oil sardine fish as feedstock

This experiment focused on biodiesel production using Indian oil sardine fish as a new low-cost feedstock. Bligh and Dyer’s method was followed for oil extraction from Indian oil sardine fishes. Biodiesel was produced by KOH catalyzed transesterification reaction with a reaction temperature of 150 °C. Optimization of the process parameters influencing the biodiesel production was performed using response surface methodology (RSM). Box-Behnken experimental design was used for the statistical analysis. The effect of methanol vol%, KOH wt% and reaction time over the reaction were studied. Chemical characterization of the biodiesel produced was carried out by Gas Chromatography-Mass Spectroscopy (GCMS) analysis. Physicochemical properties of the biodiesel were characterized according to ASTM 6751 standard. The optimum process conditions for the biodiesel yield of 96.57% were found to be 20 vol% methanol, 1.25 wt% KOH and 25 min reaction time. The 150 °C reaction temperature used in this process enhances the transesterification reaction by reducing the reaction time from the normally observed 60–120 min to 25 min with a high yield of biodiesel.

Comparative study on biodiesel production from Jatropha Curcas oil by supercritical and chemical catalytic method: a mathematical approach

ABSTRACTJatropha curcas oil is a renewable raw material which has been widely used for the production of biodiesel (BD) using various processes. This research article presents a study about BD production via chemical catalytic transesterification reaction method, supercritical methanol (SCM) method, and SCM with stirrer method. On this viewpoint, mathematical models of transesterification reaction process are formulated. The model systems are solved mathematically as well as numerically and the optimum value of important parameters, including reaction temperature, stirrer speed, and the molar ratio of methanol to oil, are found out. A comparative mathematical study has been made among these three processes with respect to product efficiency, reaction conditions, and mass transfer. Furthermore, control theoretic approach is applied in mixing intensity through supercritical process for cost-effective production of BD from Jatropha curcas oil. The optimum conditions were found to be 323K temperature, 6:1 mol/mol for methanol to oil ratio, and 561 rpm for stirrer speed. It may be concluded that SCM with stirrer is a promising alternative to produce BD from Jatropha curcas oil due to its economical benefit, high productivity, and good quality of the product. The validity of the models is established by experimental results available in literature.

Techno‐economic performance of a bio‐refinery for the production of fuel‐grade biofuel using a green catalyst

AbstractThe main challenge to the wider use of biodiesel as a transport fuel has been its high cost of production. Studies have been performed to obtain the cheapest methods for biodiesel production. The calcium oxide catalyzed transesterification reaction has shown better performance for fuel‐grade biodiesel from cheaper feedstock. In this study, a calcium oxide catalyzed biodiesel production process is designed in four different scenarios based on different possible arrangements of the downstream processes.The process flow diagrams of the different scenarios were designed using Aspen Plus and Super Pro software. These process simulations were used to evaluate the techno‐economic performance of the process scenarios. Technical performance was been evaluated based on the quantity and quality of the biodiesel and glycerol produced, the amount of biodiesel produced per amount of feedstock consumed, and the amount of other valuable byproducts. Similarly, the economic performance of the process scenarios has also been assessed using parameters such as total investment cost, unit production cost, net present value, internal rate of return, payback time, and return on investment.Each of these four scenarios was divided into two production capacity levels to investigate the effect of change in production capacity on the economic feasibility of the process scenarios.The scenario with consecutive centrifugations for glycerol and soap separation, and distillation for biodiesel purification, evidenced poor technical performance, whereas the double reactor scenario provided more, and better quality, product, and the economic feasibility of this scenario was good when the oil supply rate was above 4600 kg h−1. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd

Study on the comprehensive utilization of city kitchen waste as a resource in China

Kitchen waste (KW) is one of the most important solid wastes in cities. The amount of KW generated in China's cities is very large per capita, and processing technology is simple. Based on a data analysis, field investigation and experimental research, KW is acidic, has high moisture content, has high organic matter content, and has a big difference in C/N ratio. It is found that comprehensive utilization of KW has great advantages by means of SWOT analysis. Complete KW resource utilization can be achieved through a comprehensive treatment technology consisting of pretreatment, wet solution, oil-water separation and anaerobic digestion. Grease is converted to ester through acid catalytic pre-esterification and alkaline catalytic transesterification reaction, followed by vacuum distillation to generate biodiesel. Biological desulfurization was effective in purifying the biogas. The comprehensive treatment products include biodiesel and biogas. This study has important guiding significance for the treatment of KW.

Regeneration of geothermal-sludge based sodium silicate catalyst for transesterification of palm oil with methanol

Sodium silicate synthesized from geothermal sludge of a geothermal power plant in Indonesia was applied as a solid catalyst to catalyze transesterification reaction of palm oil with methanol. In our previous study, it has been found that the catalyst deactivated due to hydrocarbon contamination on its surface. In the present work, 3 (three) different regeneration methods were studied for reactivation of the catalyst. The studied methods were: 1) calcination at 400oC for 3 hours with a ramp of 20°C/minutes, 2) 1x-washing with methanol at room temperature, and 3) 3x-washing with methanol at 60°C. The performance of the catalyst was studied by sequential reaction batches to monitor the reaction yield from time to time. The sequence consisted of 4 (four) transesterification reaction cycles, with a catalyst regeneration process before reused in subsequence cycle. Experimental results showed that although none of the regeneration processes regained catalyst activity as high as that of the freshly-activated catalyst, the third regeneration method, i.e. 3x-washing with methanol at 60°C regained higher catalyst activity compared to the other two studied methods. The method could maintain the reaction conversion at about 50% after four cycles of reaction and regeneration, Furthermore, the kinetics of the catalytic transesterification reaction was studied by fitting the experimental data with calculated yield obtained from mathematical modelling. It was found that among the first, second, and third order reaction kinetics, the experimental data was best fitted by the calculated results from the first order reaction kinetics. Results from this work suggested that even though 3x-washing regeneration of sodium silicate catalyst with methanol at 60°C offered relatively high reactivation, further study for improvement is still needed.

In depth investigation of bi-functional, Cu/Zn/γ-Al2O3 catalyst in biodiesel production from low-grade cooking oil: Optimization using response surface methodology

Environmental concerns in fossil fuel depletion intensified the search for alternate fuel from renewable resources. The focus of this study is to produce biodiesel from low-grade cooking oil by using Cu/Zn/γ-Al2O3 as bi-functional heterogeneous base catalyzed transesterification reaction. The investigation of Cu/Zn/γ-Al2O3 catalyst on the calcination temperatures, dopant ratios to zinc oxide based and number of alumina coatings had significantly affected the catalytic performance. The physicochemical properties examined by XRD, XPS and TEM analyses over Cu/Zn/γ-Al2O3 catalyst indicates polycrystalline structure dominated by cubic Al2O3, hexagonal ZnO and monoclinic CuO species that presumably acted as active species which contributed to the catalytic transesterification of biodiesel. The design of experiments was performed using Box-Behnken design coupled with response surface methodology in order to optimize Cu/Zn (10:90)/γ-Al2O3 catalyst preparation conditions. The experimental value achieved 88.82% production of biodiesel that closely agreed with the predicted value from RSM.

Statistical optimization and kinetic study on biodiesel production from a potential non-edible bio-oil of wild radish

The bio-oil extracted from wild radish seeds is non-edible and it still remains an unexplored area in terms of its use as a feedstock for biodiesel. It was extracted from the seeds using mechanical expeller and the oil yield was found to be 46.2 ± 2 wt%. The physical and chemical properties of the extracted oil were analyzed as per AOAC official methods. In this current study, biodiesel was derived by catalytic transesterification reaction. The parameters that influence the processes like methanol to oil molar ratio, catalyst concentration, reaction temperature, and reaction time were optimized. Taguchi statistical method and Analysis of Variance (ANOVA) table were used to understand the effects of the influencing parameters and to optimize the biodiesel yield. Further, it was compared with Box-Behnken Design (BBD) using Response Surface Methodology (RSM). It shows that Taguchi method gave similar results of RSM within a limited number of runs. At optimized condition, the yield of biodiesel was 94.58 wt%. Kinetic studies were also performed for transesterification reaction and it was observed that the reaction follows pseudo-first-order kinetics. The reaction rate constants and activation energy were determined. The physical and chemical properties of the biodiesel were analyzed as per ASTM test methods and compared with ASTM D6751 standard.