Transesterification Reaction Of Vegetable Oils Research Articles

Pregled proizvodnje biodizela transesterifikacijom esterifikovanog ulja Carica Papaia (CSO)

As a result of global urbanization and modernization, the use of petroleum (fossil fuel) is on the increase and there are growing concerns among stakeholders in the oil and gas industry over the depletion rate of petroleum reserves and its rising cost. The conversion of readily available sources of biomass to produce different types of biofuels to address the future energy crisis is one of the preferred attractive choices. Biodiesel is generally produced by the transesterification reaction of vegetable oils, waste vegetable oil or animal fats in the presence of a suitable catalyst. The choice of biodiesel as a preferred renewable source of energy was based on its biodegradability, non-toxic, lower emissions, sulphur free, low levels of polycyclic aromatic hydrocarbons (PAHs) and their nitrated compounds. This alternative source of energy is environmentally friendly and could be used in the existing diesel engines with little or no modifications. This will reduce the world's dependence on fossil fuels that are non-renewable with the attendant environmental benefits to mankind. However, the use of these edible vegetable oils will put pressure on the food uses of such oil which will result to fuel-food crisis in the future. This impending crisis can be readily averted by exploring non-edible crops/agricultural waste biomass that can be grown or harnessed domestically and capable of producing oils as valuable raw materials for the emerging industry. A free fatty acid (FFA) lower than 3% is necessary to carry out the base catalysed reaction to end. For biodiesel production, the higher the acid value of the oil, the lesser the conversion efficiency hence the need for esterification process. Papaya seed contains 27.3% to 28.3% protein, 28.2% to 30.7% lipids, and 19.1% to 22.6% crude fibers, it is not economically used. The majority of seeds are produced as residues and discarded as agricultural waste during fruit processing, generating environmental issues. Oil is abundant in papaya seeds (13.9% to 40.0%), which is rich in monounsaturated fatty acids and beneficial phytochemicals as tocopherol, carotene, and phenolics. This provides information on how to reduce pollution and make waste seeds lucrative. As a result, the CPSO is receiving an increasing amount of attention.

BaO as a heterogeneous nanoparticle catalyst in oil transesterification for the production of FAME fuel

Metal oxide-based catalysts play an important role in the transesterification reaction of vegetable oils for fatty acid methyl ester (FAME) production. Additionally, nanocatalysts demonstrate high efficiency due to their increased surface area, higher catalytic activity, and easy operational procedures. Thus, the main objective of this work is to investigate FAME production from sunflower oil using barium oxide (BaO) nanoparticles. BaO was synthesized through one-pot sol–gel reactions and was analysed by several techniques, such as X-ray diffraction (XRD), transform infrared spectrometry (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray fluorescence(EDXRF), N2 adsorption–desorption of liquid nitrogen at 77 K [Brunner–Emmett–Teller (BET)] for surface area measurement and UV–Vis spectroscopy. BaO behaved as an efficient catalyst in the transesterification of oils into FAMEs. Furthermore, the impacts of a variety of reaction parameters on the biofuel yield were explored. The catalyst with 4.7 wt% has the maximum yield of 78.38 % achieved under the optimized reaction conditions (70 °C, 1:20 M ratio of oil:methanol). The characteristics of the resulting methyl ester partially agreed with international FAME standards, making it suitable for use as a blend with petroleum diesel in proportions defined by volume according to the specifications of the American Society for Testing and Materials(ASTM). The catalyst was also evaluated for reusability tests, and the reusability through the reaction showed less than a 7 % conversion drop after 3 runs and 14.6 % after 5 runs.

Synthesis of delafossite CuCrO2 via solution combustion method and its acid functionalization for biodiesel production

CuCrO2 was synthesized by solution combustion synthesis (SCS) and applied as a heterogeneous catalyst to produce soybean biodiesel. The combustion reaction was carried out using urea as a fuel, and copper (II) and chromium (III) nitrates as precursors. After the powders’ obtention, these were calcined and functionalized in an acidic medium. The powders were characterized by thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), and infrared spectroscopy (IR) techniques. The TG curve revealed that the formation of the CuCrO2 in the combustion reaction remained stable up to 1000 °C. The XRD results confirmed the formation of the CuCrO2 compound. The SEM images showed that the crystallinity of the samples increased after the calcination process. The IR spectra showed the presence of delafossite characteristic bands. After the transesterification reaction, biodiesel was obtained with a yield of around 80%. Thus, catalysts based on delafossite synthesized through the combustion method and functionalized showed to be promising for the transesterification reaction of vegetable oils.

Process design and simulation of industrial-scale biodiesel purification using membrane technology

Biodiesel is commonly produced through a transesterification reaction of vegetable oil with alcohol in the presence of a catalyst to produce fatty acid methyl ester (FAME). The reaction also produces glycerol as a by-product that must be separated from the FAME to obtain a biodiesel product that meets international standards. The common method to remove glycerol from FAME is washing with water. However, it produces a vast amount of wastewater and consumes much energy. Membrane technology is a promising separation technique for removing glycerol from biodiesel on an industrial scale since the separation using membrane does not produce wastewater and the energy consumption is low. In this work, the application of membrane technology to separate biodiesel and glycerol was studied through a process design and simulation of an industrial scale biodiesel purification process with a production capacity of 723 kL/day. A multistage feed-and-bleed microfiltration membrane system was designed to purify biodiesel from glycerol, and the process simulation was carried out using computer programming. The result of the process simulation showed that purified biodiesel could be produced by using the multistage microfiltration membrane system. The minimum membrane area required for the separation process in each stage could be calculated using the computer program. It was found that the total membrane area decreased with the increasing number of stages. A reduction of the total membrane area of 37% was achieved using ten stages microfiltration system. The optimum number of the stages could be determined through a tradeoff analysis of the cost to minimize the capital cost of the multistage membrane system. For the case study in this work, a stage number of 4 was found as the optimum stage number of the microfiltration system. This result showed that the membrane technology has great potential to be applied for the industrial-scale biodiesel purification process.

СРАВНЕНИЕ МАТЕМАТИЧЕСКИХ МОДЕЛЕЙ КИНЕТИКИ РЕАКЦИЙ ПОЛУЧЕНИЯ БИОДИЗЕЛЬНОГО ТОПЛИВА

Several different mathematical models describing the process of biodiesel production from triglycerides during the transesterification reaction of vegetable oil with monohydric alcohols (methanol, ethanol) were investigated and compared. The analysis revealed the difficulty of comparing different mathematical models and the lack of a unified approach to modeling the process under study. The most accurate of all analyzed models to describe and predict the progress of this process is the Schwartz model

Plasma-assisted catalytic route for transesterification reactions at room temperature

Biodiesel has been currently obtained from the transesterification reaction of vegetable oils, including residual oil as waste cooking oil (WCO), and usually in the presence of a catalyst. Advanced methods, such as plasma, have been studied to produce biodiesel since it allows for a milder conditions, mainly by decreasing both reaction temperature and time of production. The objective of this work is to investigate the plasma-assisted catalytic route for the monoesters transesterification reactions. H3PMo and NaOCH3 were used as acid and basic catalysts, respectively. The batch plasma reactor used in this work was composed by a borosilicate glass tube with concentric electrodes, in which ethyl acetate and methanol were feed. The effects of the plasma associated with both acid and basic catalysts were investigated in the ambient temperature and atmospheric pressure. In general, plasma-assisted catalytic routes showed higher ethyl acetate conversions, when compared to the routes with no plasma under the same experimental conditions. For example, the ethyl acetate conversion increased from 38% to 77% when plasma is assisting the acid catalytic reaction during 90 min. This level of conversion is comparable with values achieved for the reaction in the presence of basic catalyst without plasma, although in a shorter time of reaction. The synergistic effect between the plasma and the catalysts provided an increase in the reaction rate constants, and high ethyl acetate conversions in shorter reaction times. These findings indicate the plasma-assisted catalyst routes as promising for the production of biodiesel under room temperature, especially for the production from waste oils, which requires the use of acid catalysts and usually under extreme conditions.

The Effect of the Activation Process and Metal Oxide Addition (CaO, MgO, SrO) on the Catalytic and Physicochemical Properties of Natural Zeolite in Transesterification Reaction.

This work provides valuable information about unexplored catalytic systems tested in the transesterification reaction of vegetable oil with methanol. It was demonstrated that natural zeolite treatment leads to enhanced catalytic activity and yield of biodiesel production. The activation of the catalytic material in a mixture of 5% H2–95% Ar resulted in an improvement of the values of the TG conversion and fatty acid methyl esters (FAME) yield. In addition, it was proven that the incorporation of CaO, MgO and SrO oxides onto the natural zeolite surface improves the TG conversion and FAME yield values in the transesterification reaction.

Percentage Analysis Mixed of CPO, Phosphic Acid and Sodium Hydroxide as a Replacement for Diesel Engine Oil Fuel Using a Calorize Test

One of the researches being developed is to produce methyl esters from CPO through transesterification reaction of vegetable oil (triglycerides) with methanol. Biodiesel from crude palm oil is a new hope for answering some of the energy needs. know the rate of combustion of the biodiesel produced. Biodiesel that is produced from a mixture of CPO, phosphoric acid and sodium hydroxide, with a percentage of I. 98% CPO, 1% Phosphoric Acid, 1% Sodium Hydroxide: II. 95% CPO, 2% Phosphoric Acid, 3% Sodium Hydroxide: III. 95% CPO, 3% Phosphoric Acid, 2% Sodium Hydroxide. The results showed that the most effective mixture was 95% CPO, 3% acid phosphate and 2% sodium hydroxide with a burning rate of 0.309 g / minute in 30.42 minutes with a final temperature of 57 (oC).

Application of Activated Carbon to Obtain Biodiesel from Vegetable Oils

The methanolysis of refined vegetable oils (rapeseed oil, sunflower oil, corn oil and olive oil) using a heterogeneous carbonaceous catalyst was studied. Activated carbon (AC) was prepared from beech tree wood and used as the support for KOH and a lipase catalyst. The reactions were carried out for 1–4 h at 60 °C with a methanol-to-oil molar ratio of 6:1 and 0.5–1.5 wt.% KOH/AC. In contrast, the biotransformation of vegetable oils was carried out for 24 h at 40 °C with an alcohol-to-oil molar ratio of 4:1 and 5 wt.% lipase/AC. The highest methanolysis yield (99%) for the fatty acid methyl esters was obtained for lipase/AC. These data show that activated carbon is a promising supporter for KOH as well as for lipase in the transesterification reaction of vegetable oils with methanol. The use of both catalysts in the transesterification reaction may improve biodiesel production. The lipase/AC enables the reduction in methanol excess and eliminates waste formation, whereas the saponification of triglycerides is scanty when KOH/AC is used.

Constrained iterative learning control of batch transesterification process under uncertainty

Biodiesel are fatty acid methyl esters (FAME), which can be produced by the transesterification reaction of vegetable oils with methanol. A batch transesterification process is often associated with model uncertainties and unmeasured disturbances, which may create a detrimental effect on the batch end FAME yield due to plant-model mismatch. Therefore, batch-to-batch iterative learning control (ILC) is necessary to track the desired reference FAME profile under such process variations. This work demonstrates a constrained quadratic programming problem (QPP) based batch-to-batch ILC framework for optimizing the endpoint FAME concentration by controlling the hot water flow profile passing through the reactor jacket under uncertainty. Parametric uncertainties are modeled separately in two case studies, which involve different batch transesterification models differing in the state variables. Case study 1 considers uncertainty in the apparent activation energy and brings out a comparative study between a QPP based ILC and a heuristics based approach. The comparison is shown based on the tracking performance of the ILC in terms of reduction in the batch end tracking error and total root mean square error of the same. Batch-to-batch ILC is superior as it produces faster convergence of the tracking error by saving 6 batches as compared to the heuristics approach. Case study 2 involves the implementation of constrained QPP based ILC algorithm on a proposed 54-state detailed batch transesterification model of canola oil, where uncertainty is modeled as the change in the input triglyceride composition from the base case. The desired reference FAME concentration profile is tracked in 9 batches for fixed uncertainty whereas it takes 15 batches to achieve the stochastic convergence under stochastic disturbance.

The Carbon Effect in Biodiesel Synthesis

Biodiesel is synthesized from the trans-esterification reaction of vegetable oil and alcohol using a catalyst such as acids, bases or enzymes. The acid catalyst that is often used is sulfuric acid; H2SO4, and HCl while most of base catalysts are NaOH and KOH. The aim of this study is to determine the effect of carbon derived from sugar heating in the synthesis of biodiesel with a sulfuric acid catalyst; H2SO4. Trans-esterification reaction of Jatropha oil and methanol with sulfuric acid catalyst was done with oil and methanol at 1:9 ratio. The results showed that (1) the physical properties of the biodiesel was synthesized with carbon-H2SO4 has a difference with physical properties the biodiesel was synthesized by sulfuric acid (2) carbon-H2SO4 was used in the trans-esterification reaction of Jatropha oil and methanol to produce methyl ester character is the density of 0.889 g / mL, 24.59 cSt viscosity and refractive index of 1.464, (3) methyl ester produced from the reaction of trans-esterification of Jatropha oil and methanol with sulfuric acid catalyst has a character that is a density of 0.882 g / mL, 11.70 cSt viscosity and refractive index of 1.458.

EVALUATION OF THE USE OF GLYCERIN AND SODIUM SILICATE IN WATER-BASED DRILLING FLUID

Glycerin is a by-product of the transesterification reaction of vegetable oil to produce biodiesel. Glycerin production has increased as the number of biodiesel industries has grown. With features such as water solubility, low cost, and non-toxicity, it is a good substance for water-based drilling fluid formulations with less environmental contamination. The experiments were conducted using a drilling fluid commonly used in Brazil and were compared with glycerin additions at concentrations of 5, 10, 15, and 20% by volume. Considering that as a result of the raw materials used, the biodiesel production routes produce a contaminated glycerin, it was decided to use a bi-distilled glycerin. In addition, sodium silicate, which uses industrial water or seawater, was added as a corrosion inhibitor due to its good performance and environmental non-toxicity. The sodium silicate was effective in combating corrosion without interfering with the fluid properties. The values of plastic viscosity, yield point, L3 (reading 3 rpm), and gel strength, mostly presented results equal to or better than the original formulation of the fluid used as a comparison.

Comparative Evaluation of Thermogravimetric and Refractive Index Techniques in Determining Biodiesel Yield

Biodiesel is a clean and renewable resource that consists of mono-alkyl esters of long chain fatty acid, which could be obtained from the transesterification reaction of vegetable oils and animal fats with alcohols and catalysts. Biodiesel yield has typically been determined using expensive and laborious techniques. The attempt of this study was to examine the potential of quantifying the biodiesel conversion in real time using refractive index in transesterification process of canola oil with methanol and KOH. Biodiesel yields at five different mixing intensities and reaction times were measured using a refractometer. The measured results were then compared with analytical data obtained from thermogravimetric analysis (TGA) technique over a temperature range of 25℃ - 600℃. Experimental results indicated that the FAME conversions at different mixing intensity and reaction time measured from refractometer correlated well to the relative weight losses from TGA method with R2 = 0.93 (p ≤ 0.05); however, the refractometer may over-estimate the biodiesel yield when the reaction rate was too low. Overall, the refractometer technique is cheaper and easier to manage and could provide a reliable prediction of biodiesel yield in real time.

Mathematical Modeling of the Transesterification Reaction by Finite Elements: Optimization of Kinetic Parameters Using the Simplex Sequential Method

The use of biodiesel as fuel has been presented as a viable alternative in the search for renewable energies. It can be produced from the transesterification reaction of vegetable oils with methanol in the presence of sodium or potassium hydroxide as catalysts. In the present research, the transesterification reaction of soybean oil was modeled considering the three steps of the direct and reverse reactions following a second order general kinetics by the finite element method using the COMSOL Multiphysics® software. The values of rate constants were determined using the simplex optimization method coupled with the desirability functions. The optimized rate constants for the forward reactions were 0.250 × 10−6 (k1f), 1.137 × 10−6 (k2f) and 3.134 × 10−6 (k3f); and for the reverse reactions were 0.202 × 10−6 (k1r), 0.884 × 10−6 (k2r) and 0.219 × 10−6 (k3r) all in m3mol−1s−1. The kinetic model proposed for the reaction can be simulated by the finite element method (FEM) under realistic conditions.

Biodiesel at the Crossroads: A Critical Review

The delay in the energy transition, focused in the replacement of fossil diesel with biodiesel, is mainly caused by the need of reducing the costs associated to the transesterification reaction of vegetable oils with methanol. This reaction, on an industrial scale, presents several problems associated with the glycerol generated during the process. The costs to eliminate this glycerol have to be added to the implicit cost of using seed oil as raw material. Recently, several alternative methods to convert vegetable oils into high quality diesel fuels, which avoid the glycerol generation, are being under development, such as Gliperol, DMC-Biod, or Ecodiesel. Besides, there are renewable diesel fuels known as “green diesel”, obtained by several catalytic processes (cracking or pyrolysis, hydrodeoxygenation and hydrotreating) of vegetable oils and which exhibit a lot of similarities with fossil fuels. Likewise, it has also been addressed as a novel strategy, the use of straight vegetable oils in blends with various plant-based sources such as alcohols, vegetable oils, and several organic compounds that are renewable and biodegradable. These plant-based sources are capable of achieving the effective reduction of the viscosity of the blends, allowing their use in combustion ignition engines. The aim of this review is to evaluate the real possibilities that conventional biodiesel has in order to success as the main biofuel for the energy transition, as well as the use of alternative biofuels that can take part in the energy transition in a successful way.

Ultrasound affects the selectivity and activity of immobilized lipases applied to fatty acid ethyl ester synthesis

Hydrophobic carriers can be used to improve the activity, stability and other properties of enzymes. Physical agents, like ultrasound, may also contribute to improving the dispersion and collision of the reagent molecules, decreasing the reaction time and intensifying the catalytic process. However, its effect on the enzyme activity and reaction selectivity is still not entirely understood. Here, enzyme modulation of immobilized lipases was studied under pulsed ultrasound irradiation in fatty acid ethyl ester (FAEE) synthesis for biodiesel production. Novozym 435® and two commercial lipases from Thermomyces lanuginosus and Rhizomucor miehei, immobilized on Octadecyl-Sepabeads were used as a biocatalyst in the transesterification reaction of vegetable oils and ethanol. The use of ultrasound associated with catalysis by the Novozym 435 increased the production of FAEE by about three times (from 8.9 to 26.4%) using soybean oil and changes were observed in the profile of the products. From the sonicated reaction, ethyl-palmitate production decreased from 23.4 to 11.7%, while the ethyl-linoleate content rose from 47.5 to 59.2%. On the other hand, the T. lanuginosus lipase was less affected by sonication with the overall production of FAEE increasing from 17.2 to 24.1%, with ethyl-palmitate and ethyl-linoleate content changing from 16.2 to 17.5% and 55.0 to 47.8%, respectively. Although the changes in the production yield are not too high, the main idea here was to show that ultrasound modulates the lipase activity as well as its respective selectivity. Thus, ultrasound, is responsible for changing the ethyl ester production, which can be applied to many other biochemical processes to improve or modulate their synthesis yield.

Multi-objective optimization of integrated biodiesel production and separation system

Biodiesel is a mixture of fatty acid methyl esters (FAME), which can be produced by the transesterification reaction of vegetable oils with methanol. The production of biodiesel is comprised of a series of stages such as reaction, methanol separation, water washing, decantation, and unreacted oil separation followed by the biodiesel purification. Each of these stages involves certain performance measures which need to be optimized for making the overall process cost-effective and productive. Therefore, a commercial base catalyzed batch transesterification process is optimized first with an objective: maximization of the fatty acid methyl esters concentration in final batch time. Dynamic optimization is used with the hot water flow rate passing through the reactor jacket as the decision variable. Orthogonal collocation on finite elements (OCFE) method is employed to convert the dynamic optimization problem into a non-linear programming (NLP) problem. The integrated reaction-separation steps of the biodiesel production process is modeled and simulated in Aspen Plus. Total two multi-objective optimization (MOOP) problems are formulated and solved to capture the trade-offs among the performance indices of the reactor and separation units collectively. Compared to the dynamic optimization problem result, MOOP-1 produced an optimal biodiesel concentration of 0.97 kmol/m3 at an optimal reactor energy cost of 0.12 $/l FAME produced. MOOP-2 determined that the energy expenditure in the reactor jacket is 1.064 times the total energy usage of all the reboilers of the distillation columns. In comparison to MOOP-1, the Pareto-fronts of MOOP-2 produced more cost-effective results in terms of comprehensive trade-offs among the objective functions used.

Synthesis of solid catalyst from egg shell waste and clay for biodiesel production

Until now, energy consumption in Indonesia is almost entirely fulfilled by fossil fuels, thus, its availability will be limited and continue to decrease. To overcome these problems, development and utilization of renewable energy are required, one of which is biodiesel. Biodiesel can be prepared through transesterification reaction of vegetable oil using catalyst. In this research, a solid catalyst for biodiesel synthesis was prepared from chicken egg shell waste and clay. Optimization of the transesterification reaction of coconut (Cocos nucifera) oil to obtain biodiesel was also carried out. The formation of CaO/kaolin catalyst was confirmed based on the results of XRD and SEM-EDS. This catalyst is suitable for biodiesel synthesis from vegetable oils with lower FFA (free fatty acid) levels, i.e. coconut oil with FFA level of 0.18%. Based on FTIR result, FFA level and flame tests, it was found that biodiesel was successfully formed. Synthesis of biodiesel has the optimum conditions on reaction time of 16 hours and temperature of 64 °C, with oil: methanol ratio of 1: 15 and CaO/kaolin catalyst concentration of 0.9% in a reflux system.

Monitoring the Transesterification Reaction of Vegetable Oil to Biodiesel by Fluorescence Spectroscopy with UV Excitation: Correlation with Viscosity

The transesterification reaction is the most widely used process for biodiesel production. Monitoring it in real time enables optimization of the operational parameters, hence providing better yields and lowering the costs of biodiesel production. Techniques that have been used for this purpose include chromatography and spectroscopic methodologies. In this work, transesterification reactions were monitored on line, in situ, by fluorescence spectroscopy with ultraviolet excitation at ~360 nm. The temporal behavior of the fluorescence intensity was similar to that of the viscosity of the oil/alcohol/catalyst solution, as reported in the literature. The results indicated that UV-Vis fluorescence spectroscopy could be used on-line, in situ, for the efficient monitoring of biodiesel production, providing a valuable indication of the degree of success of the transesterification reaction. DOI: http://dx.doi.org/10.17807/orbital.v10i1.1026

Conformation Analysis of T1 Lipase on Alcohols Solvent using Molecular Dynamics Simulation

Biodiesel usually is produced commercially via a transesterification reaction of vegetable oil with alcohol and alkali catalyst. The alkali catalyst has some drawbacks, such as the soap formation during the reaction. T1 Lipase enzyme had been known as a thermostable biocatalyst which is able to produce biodiesel through a cleaner process. In this paper the performance of T1 lipase enzyme as catalyst for transesterification reaction in pure ethanol, methanol, and water solvents were studied using a Molecular Dynamics (MD) Simulation at temperature of 300 K for 10 nanoseconds. The results have shown that in general the conformation of T1 lipase enzyme in methanol is more dynamics as shown by the value of root mean square deviation (RMSD), root mean squared fluctuation (RMSF), and radius of gyration. The highest solvent accessible surface area (SASA) total was also found in methanol due to the contribution of non-polar amino acid in the interior of the protein. Analysis of MD simulation has also revealed that the enzyme structure tend to be more rigid in ethanol environment. The analysis of electrostatic interactions have shown that Glu359-Arg270 salt-bridge pair might hold the key of thermostability of T1 lipase enzyme as shown by its strong and stable binding in all three solvents.