Transesterification Of Sunflower Oil Research Articles

Optimization of Dissolved Air Flotation (DAF) process for the treatment of oily water from biodiesel production

Biodiesel production has become one of the most efficient ways of diversifying the energy matrix. However, the increase in biodiesel production increases the generation of wastewater. Therefore, this study aimed to characterize the wastewater generated in the biodiesel washing process, obtained by the alkaline transesterification of sunflower oil, and to evaluate its treatment by the dissolved air flotation (DAF) system, using a Central Composite Rotational Design (CCRD). The first DCCR was carried out with 4 independent variables: pH, Coagulant Dose (CD), Polymer Dose (PD), and Recirculation Rate (RR), with the response variables being apparent color removal and turbidity removal. Based on the results of the first DCCR, optimization tests were designed with DC and DP as independent variables and apparent color, turbidity, COD, and oil and grease (OG) as response variables. The process showed high apparent color and turbidity removal efficiency. The best results were obtained in tests 10 (DC = 1545 mg.L-1 and DP = 1050 mg.L-1) and 3 (DC = 700 mg.L-1 and DP = 8.8 mg.L-1), with the removal of 99.88% and 99.22%, respectively. For the COD and OG parameters, the best results were observed in tests 8 (DC= 555 mg.L-1 and DP= 6 mg.L-1) and 5 (DC= 1050 mg.L-1 and DP= 6 mg.L-1), with 98% and 99.42% removal, respectively. FAD treatment using the combination of coagulant and cationic polymer proved to be highly efficient in treating wastewater from biodiesel production.

Bio-Based Polyurethane Networks Containing Sunflower Oil Based Polyols.

This work focused on the preparation and investigation of polyurethane (SO-PU)-containing sunflower oil glycerides. By transesterification of sunflower oil with glycerol, we synthesized a glyceride mixture with an equilibrium composition, which was used as a new diol component in polyurethanes in addition to poly(ε-caprolactone)diol (PCLD2000). The structure of the glyceride mixture was characterized by physicochemical methods, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), nuclear magnetic resonance spectroscopy (NMR), and size exclusion chromatography (SEC) measurements. The synthesis of polyurethanes was performed in two steps: first the prepolymer with the isocyanate end was synthesized, followed by crosslinking with an additional amount of diisocyanate. For the synthesis of the prepolymer, 4,4'-methylene diphenyl diisocyanate (MDI) or 1,6-hexamethylene diisocyanate (HDI) were used as isocyanate components, while the crosslinking was carried out using an additional amount of MDI or HDI. The obtained SO-PU flexible polymer films were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The so-obtained flexible SO-PU films were proved to be suitable for the preparation of potentially biocompatible and/or biodegradable scaffolds. In addition, the stress versus strain curves for the SO-PU polymers were interpreted in terms of a mechanical model, taking into account the yield and the strain hardening.

Supported sodium aluminate catalysts effectively catalyze biodiesel synthesis

Strongly basic sodium aluminate (NaAlO2) was supported on titanium dioxide, γ-alumina, and hydrotalcite by impregnation. The resulting catalysts showed improved specific activity in the transesterification of sunflower oil in methanol, as compared to the unsupported NaAlO2. Even with small sodium aluminate loading (i.e. 2.3% up to 9.4%) valuables fatty acid methyl esters (FAME) yields can be obtained. In particular, 9.4SA-HT shows the best catalytic activity achieving a 70% yield after 240 min of reaction, with a mere catalyst loading of 1.5% wt (with respect to the oil mass) in the reaction media. Innovatively, a detailed correlation between the amount, strength, and nature of the basic sites and the support type is proposed. In particular, it is demonstrated that only a part of the basic sites is effectively available for catalysis because of the already adsorbed atmospheric CO2. Thus, a combination of effective availability and strength of the active species is pivotal for a high catalytic performance in the synthesis of biodiesel from triglycerides.

Utilization of Salmon fish bone wastes as a novel bio-based heterogeneous catalyst-support toward the production of biodiesel: Process optimizations and kinetics studies

This study investigated the feasibility of using calcined Salmon fish bone wastes as an inexpensive and reusable catalyst-support for the biodiesel production via transesterification of sunflower oil. In this venue, a series of catalysts were synthesized by impregnating potassium hydroxide (KOH) onto the calcined Salmon fish bones. The as-prepared catalysts were characterized through several techniques, including the FESEM, BET-BJH, TGA, FT-IR, and XRD. In this regard, the effects of the calcination temperature of the waste Salmon fish bone, KOH loading amount, and the calcination temperature of KOH-impregnated support upon the catalytic activity of the final catalyst were understudied. Results displayed that the calcination temperature of fish bones at 1273 K with 40 wt% of KOH loading, which was calcined at 873 K, led to the highest catalytic performance. For this optimum material, the effects of the parameters, such as the catalyst loading, the methanol: oil molar ratio, and the reaction time and temperature upon the biodiesel production yield were examined. It was determined that the optimum operating conditions for the reaction included the catalyst loading of 10 wt%, the methanol: oil molar ratio of 10:1, and the reaction temperature of 338 K for 3 h. The gas chromatography and 1HNMR analyses revealed an optimum biodiesel production yield of 99.13 %. This result is attributed in part to a rather high basicity of the aforementioned optimum material. Moreover, this optimum species was shown to endure four consecutive reaction cycles, whereas its activity dropped by about 10 %. Furthermore, the chemical kinetic parameters of the reaction using this catalyst were determined to be; the reaction rate constant of 0.45 h−1 and its respective activation energy of 67.01 kJ/mol. Ultimately, it was demonstrated that neither internal nor external mass transfer limitations existed in the heterogeneous system considered in this research hence, all observed behaviors were solely due to chemical kinetics.

Towards Photothermal Acid Catalysts Using Eco-Sustainable Sulfonated Carbon Nanoparticles—Part I: Synthesis, Characterization and Catalytic Activity towards Fischer Esterification

The development of photothermal catalysts for biodiesel synthesis reaction (transesterification) requires the production of light-absorbing nanoparticles functionalized with catalytic (acid) groups. Using Stöber method, it is possible to produce resorcinol/formaldehyde resin (RF) nanoparticles, which can be carbonized (pyrolysis in an inert atmosphere) and sulfonated. In this work, vegetable tannins are used as a replacement for synthetic resorcinol in the Stöber synthesis of resin (TF) nanoparticles. The nanoparticles are characterized using DLS, FESEM, TEM and N2 adsorption-desorption isotherms. Both resin and carbon nanoparticles are sulfonated by reaction with concentrated sulfuric acid. The attachment of sulfonic groups is verified by FTIR and EDX. The number of sulfonic groups is measured by acid/base titration and TGA. All sulfonated nanoparticles show catalytic activities towards Fischer esterification of ethanoic acid with ethanol, and high (up to 70%) conversion is obtained. The conversion is lower with TF-based nanoparticles, but the turnover numbers are similar in the RF- and TF-based materials. Sulfonated carbon and resin nanoparticles show higher catalytic activity compared to commercial acidic catalysts (e.g., Nafion®). Photothermal heating of carbon nanoparticles is observed. In Part II, sunflower oil transesterification, catalyzed by sulfonated nanoparticles, is observed. Photothermal catalysis of acetic acid esterification and sunflower oil transesterification is demonstrated.

The assessment of sustainability indicators for triglycerides transesterification with alcohols catalyzed by ion exchange resins

The research was aimed at determining the dependences of sustainability indicators on the parameters of the sunflower oil transesterification with ethyl, propyl, and butyl alcohol catalyzed by anion exchange resin AV-17-8 with OH– ions or cation exchange resin KU-2-8 with H+ or immobilized Zn2+, Sn2+, Ni2+, Co2+, and Cu2+ ions. Such sustainability indicators as the E-factor, atomic efficiency, mass intensity and mass productivity, reaction mass efficiency, stoichiometric factor, etc., have been determined. We established that sustainability indicators of transesterification catalyzed by ion exchange resins depend on the yield of higher fatty acid esters that can be achieved by immobilized metal ions. The unreacted alcohol regeneration significantly reduces the E-factor value and increases the reaction mass efficiency. During the sunflower oil ethanolysis, the minimum E-factor value is achieved at the ethyl alcohol:triglyceride molar ratio corresponding to the maximum yield of higher fatty acid esters. The reaction mass efficiency calculated without considering the unreacted alcohol regeneration is one of the criteria for determining its regeneration expediency. The sustainability indicators are the additional criteria for selecting optimal conditions of the sunflower oil transesterification with aliphatic alcohols catalyzed by ion exchange resins. The calculated sustainability indicators indicate that the investigated ion exchange resins as heterogeneous transesterification catalysts provide a high yield of higher fatty acid esters. Using the researched catalysts ensures a low E-factor, making the process environmentally friendly.

Synthesis of Biodiesel from Sunflower Oil Using the Calcium Carbide Dust as a Solid Catalyst

The developed solid catalyst from calcium carbide dust (CCD) with potassium nitrate is investigated for transesterification of sunflower oil to biodiesel or fatty acid methyl ester (FAME). The objective of this study is to develop the solid catalyst from CCD and test it at various operating parameters such as wt. % of KNO3/CCD, molar ratio of methanol to oil, reaction time and reusability of the modified solid catalyst with a fixed reaction temperature of 60 °C and 3 wt. % of catalyst loading. The FAME yield was up to 97 wt. % with 15 wt. % of KNO3/CCD, 15:1 methanol-to-oil molar ratio and 7 h reaction time. Unfortunately, the modified solid catalyst could not be reused after regeneration using n-hexane washing followed by recalcination at 500 °C for 3 h.

Highly efficient scallop seashell-derived catalyst for biodiesel production from sunflower and waste cooking oils: Reaction kinetics and effect of calcination temperature studies

The sustainable production of biodiesel from waste materials has become of utmost importance in recent years. In this study, cheap CaO catalysts were prepared by calcination of waste scallop seashells (Noble Pectin). The seashells were thermally treated at different temperatures (600–1000 °C) and then used in the transesterification of sunflower oil for biodiesel production. The catalysts were characterized using Fourier Transform Infrared Spectroscopy (FTIR) and simultaneous Thermal Gravimetric-Differential Scanning Calorimetry (TG-DSC) techniques. The highest Fatty Acid Methyl Esters (FAME) yield (97%) was obtained in the presence of the catalyst calcined at 700 °C under the following conditions: a methanol-to-oil molar ratio (MOMR) of 12:1, a catalyst-to-oil ratio (CTOR) of 10 wt%, a stirring rate of 700 rpm, a reaction temperature of 65 °C and a reaction time of 4 h. The seashell-derived catalyst was practically stable for at least 4 consecutive runs in the reusability study, maintaining a high FAME yield (>92%). The reaction followed pseudo-first order kinetics, with an activation energy (Ea) of 133.57 kJ/mol and a pre-exponential factor (A) of 4.025 × 1018 min−1. This catalyst additionally exhibited a very high activity in the transesterification of waste cooking oil, with a similar FAME yield of 97%. This shows that this catalyst is promising for potential biodiesel production scale-up schemes and industrial applications.

Modifications in the kinetics of transesterification of sunflower oil over strontium supported on silica by barium doping

Modifications in the kinetics of transesterification of sunflower oil over strontium supported on silica by barium doping

Combination of oscillatory and hydrodynamic system for biodiesel production from sunflower oil

In recent years, biodiesel as renewable energy has attracted much attention. The major aims of the biodiesel production method are high conversion and reduced reaction time. This study aimed to optimize biodiesel production from sunflower oil using the transesterification method in oscillatory-hydrodynamic combined systems. The dimensions of the smooth periodic constriction reactor (SPC), tube diameter (D), the diameter of constricted area (d0), and baffle spacing (l) were obtained at 5, 2, and 13 mm, respectively. The process optimization was carried out by response surface methodology. The results indicated that by increasing residence time from 30 s to 90 s, the yield was increased about 6%. By increasing the catalyst concentration from 0.75% to 1%, the yield increased approximately 6%; increasing the molar ratio from 6:1 to 9:1 increases the yield. The yield was also increased with the reaction temperature rise from 30 °C to 40 °C. Then, by increasing the temperature from 40 °C to 50 °C, the methyl ester content was increased from 81.59% to 85.75%. The optimum point was tested and compared with the ASTM D6751 standard. The results showed that transesterification of sunflower oil with this combined system could function as a good alternative to diesel.

Production of Biodiesel by Ethanolic Transesterification of Sunflower Oil on Lateritic Clay- based Heterogeneous Catalyst

Production of Biodiesel by Ethanolic Transesterification of Sunflower Oil on Lateritic Clay- based Heterogeneous Catalyst

Evaluation and kinetic study of alkaline ionic liquid for biodiesel production through transesterification of sunflower oil

Biodiesel production is performed in the industry by alkaline transesterification of oils with a low amount of free fatty acids. In order to reduce the disposal of conventional catalysts used industrially, ionic liquids (ILs) have been studied to be applied as catalysts in transesterification since they can be recovered and reused in subsequent reaction cycles. In this work, the ionic liquid choline hydroxide (ChOH) was successfully applied as a catalyst for the transesterification reaction of triacylglycerols present in sunflower oil with methanol. A kinetic modeling study under the specific conditions of 2 wt% catalyst dosage, 1:10 oil/methanol molar ratio, for 0–120 min at 35–65 ℃ was conducted, and liquid–liquid extraction with water/butanol was evaluated as a process to recover the IL. A 95.0% ester yield content was achieved in this work for a short reaction time (30 min). Furthermore, the results of the kinetic study demonstrated that a first-order model was the best fit for the reaction with a rate constant (k) estimated as 0.1182 min−1 and activation energy (Ea) of 13.64 kJ/mol. For the tested conditions, the complete recovery of the IL using liquid–liquid extraction did not occur since it is noted the presence of ChOH in both phases.

Influence of ultrasound irradiation power on surface design of CaO nanoparticles over secondary carbon-templated meso designed ZSM-5 for biofuel production from vegetable oil

A series of potential bifunctional basic/acidic CaO over hierarchical ZSM-5 nanocatalysts were synthesized and investigated in biofuel production. Secondary hard templating was applied on the ZSM-5 support by carbonaceous charcoal particles in order to increase the pore size in favour of better diffusion of the large triglyceride molecules. The ultrasound irradiation was also applied with three different powers on impregnation of CaO active phase and its effect on well dispersing the particles was investigated. FESEM images showed high distributed and smaller particles on the surface of highly sonicated catalyst compared to the non-sonicated sample and BET-BJH results confirmed the opening of the pores and therefore size and volume increase by sonication. TPD-CO2 results indicated that both secondary templating and sonication have increased the strong basic sites. The particles were also smaller and less agglomerated due to sonication as observed in TEM images. Catalytic performance tests also confirmed the effective role of secondary charcoal templating on the conversion of oil as well as the positive influence of ultrasound irradiation. Sonicated nanocatalyst was also more stable after five times of reusability tests in transesterification of sunflower oil.

Study on Kinetics and Reaction Parameters of Biodiesel Production from Sunflower Oil and Methanol Using Zinc Oxide Supported Calcium Oxide

This study investigated the effect of reaction parameter, reaction kinetics and mechanism of transesterification of sunflower oil with methanol by using CaO/ZnO heterogeneous catalyst. The influence of reaction time, molar ratio and catalyst amount and reaction temperature on fatty acid methyl esters (FAME) yield was investigated. The catalysts were prepared by incipient wetness impregnation and characterized by using X-ray diffraction (XRD) and Hammett indicator method. The FAME contents were analyzed by gas chromatography using the EN 14103 standard method. The highest FAME yield of 82% was obtained at 9/1 methanol/oil molar ratio, 3 wt.% catalyst amount and 3 hours of reaction time at 65 °C of reaction temperature by using 20% CaO/ZnO catalyst. The reaction could be considered pseudo first order with respect to triglyceride (TG). The reaction model based on Eley-Rideal mechanism was proposed where adsorbed methanol reacted with TG before desorption of glycerin. The results showed that experimental reaction rates exhibited good agreement with calculated reaction rates.

The effect of process parameters and catalyst support preparation methods on the catalytic efficiency in transesterification of sunflower oil over heterogeneous KI/Al2O3-based catalysts for biodiesel production

The essence of this study is synthesis of a newly developed and efficient heterogeneous catalyst based on aluminum oxide support promoted with potassium iodide (KI) as active dopant responsible for pronounced catalyst activity. Modified sol–gel, reflux and hydrothermal method were used for synthesis of aluminum-oxide support using aluminum isopropoxide as a precursor. The γ-Al2O3 support and KI/γ-Al2O3 catalyst samples were examined by various experimental techniques. Effects of several operational parameters were considered and those are: methanol to sunflower oil molar ratio, catalyst loadings, reaction time and reaction stirring rate. The obtained results indicated that modified sol–gel method for synthesis of γ-Al2O3 catalyst support is the most favorable for obtaining the catalyst with superior catalytic performances in transesterification of sunflower oil. A maximum conversion (triglycerides to methyl esters) of 99.99% was achieved using the SG-KI/γ-Al2O3-770 catalyst under following optimal process parameters: 15:1 methanol to sunflower oil molar ratio, 2.5 wt% catalysts loading, 600 rpm stirring rate and 4 h of the reaction run.

Transesterification of Sunflower Oil in the Presence of the Cosolvent Assisted by Hydrodynamic Cavitation

Transesterification of Sunflower Oil in the Presence of the Cosolvent Assisted by Hydrodynamic Cavitation

Optimization of Biodiesel Production from Sunflower Oil Transesterification using Ca-K/Al2O3 Nanocatalysts

In this study, an attempt was made to optimize the conditions for the transesterification of sunflower oil with methanol, catalyzed by Ca-K/Al2O3 nanocatalysts, using response surface methodology. The examined variables were reaction temperature (55, 65 and 75 °C), reaction time (1, 2, 3, 4 and 5 h), catalyst weight base oil (3, 6, 9 and 12 wt%), Ca content (20, 30, 50, 60 and 80 wt%), K content (5, 10, 15 and 20), methanol:sunflower oil molar ratio (3:1, 6:1, 9:1 and 12:1), calcination temperature (600, 700 and 800 °C) and calcination time (1, 2, 3 and 4 h). Catalyst characterization was done by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR) and temperature programmed desorption (TPD). The maximum fatty acid methyl esters (FAME) conversion efficiency (biodiesel production efficiency) was 98.3%, at a calcination temperature of 800 °C for 3 h, a methanol-to-oil ratio of 9:1, a reaction temperature of 75 °C, a reaction time of 3 h and a catalyst-to-oil mass ratio of 9%.

The effect of operating parameters of hydrodynamic cavitation – assisted alkaline catalyzed transesterification of sunflower oil with methanol on the degree of triglyceride conversion

Abstract The effect of operating parameters such as reaction mixture inlet pressure p 1 (101.3–1013.2 kPa), methanol to oil molar ratio M 1 (3–12), the concentration of catalyst C c (0.0–1.0 wt%), temperature T (25–50 °C) and the number of passes of the reaction mixture through the venturi type hydrodynamic cavitation reactor n (1–12) on alkali-catalyzed transesterification of sunflower oil with methanol assisted by hydrodynamic cavitation (ACTC) on the value of the degree of triglyceride conversion (DTC) was investigated. ACTC was performed by the venturi-type hydrodynamic cavitation reactor (VCR) of our construction. It was found that the values of DTC increase with the increase in p 1, M 1, C c, and n, and decrease with the increase in T. Cavitation yield (CY) values were calculated. The ACTC was proved to be the simplest, fastest, and most highly energy-efficient current technology for the production of biodiesel.

Enzymatic Production of Ecodiesel by Using a Commercial Lipase CALB, Immobilized by Physical Adsorption on Mesoporous Organosilica Materials

The synthesis of two biocatalysts based on a commercial Candida antarctica lipase B, CALB enzyme (E), physically immobilized on two silica supports, was carried out. The first support was a periodic mesoporous organosilica (PMO) and the second one was a commercial silica modified with octyl groups (octyl-MS3030). The maximum enzyme load was 122 mg enzyme/g support on PMO and 288 mg enzyme/g support on octyl-MS3030. In addition, the biocatalytic efficiency was corroborated by two reaction tests based on the hydrolysis of p-nitrophenylacetate (p-NPA) and tributyrin (TB). The transesterification of sunflower oil with ethanol was carried out over the biocatalysts synthesized at the following reaction conditions: 6 mL sunflower oil, 1.75 mL EtOH, 30 °C, 25 μL NaOH 10 N and 300 rpm, attaining conversion values over 80% after 3 h of reaction time. According to the results obtained, we can confirm that these biocatalytic systems are viable candidates to develop, optimize and improve a new methodology to achieve the integration of glycerol in different monoacylglycerol molecules together with fatty acid ethyl esters (FAEE) molecules to obtain Ecodiesel.

Integrated microsystems for lipase-catalyzed biodiesel production and glycerol removal by extraction or ultrafiltration

Competition among renewable energy sources in today's market is growing rapidly. Renewables have grown to the point where they are taking significant material market share from coal, gas, and uranium. Recently, biodiesel production has been intensified by lipase-catalyzed transesterification performed in microsystems. Another challenge in biodiesel production is the purification of the biodiesel. Common purification methods are usually more energy and time consuming than the biodiesel production itself.In this work, an integrated biodiesel production process composed of lipase-catalyzed transesterification of sunflower oil and product purification was performed in microreactor and microseparator units connected in series. Glycerol, the by-product of the transesterification process, was removed from the reaction mixture by two different separation methods, deep eutectic solvent extraction and membrane separation. Different integrated setups were developed and evaluated in terms of FAME yield and purity. The most promising integrated process was found to be the one combining 2-inlets feeding strategy for biodiesel production in a microreactor with a microseparator connected in series, in which a choline chloride-glycerol deep eutectic solvent was used. In this integrated system, a FAME yield of 94% and a glycerol content below 0.02% (w/w) were achieved for the residence time of 20 min.