scholarly journals Biodiesel by Transesterification of Rapeseed Oil Using Ultrasound: A Kinetic Study of Base-Catalysed Reactions

Energies ◽  
2018 ◽  
Vol 11 (9) ◽  
pp. 2229 ◽  
Author(s):  
José Encinar ◽  
Ana Pardal ◽  
Nuria Sánchez ◽  
Sergio Nogales

The objective of this work was to study the acceleration that ultrasound causes in the rate of biodiesel transesterification reactions. The effect of different operating variables, such as ultrasound power, catalyst (KOH) concentration and methanol:oil molar ratio, was studied. The evolution of the process was followed by gas chromatography, determining the concentration of methyl esters at different reaction times. The biodiesel was characterized by its density, viscosity, saponification and iodine values, acidity index, water content, flash and combustion points, cetane index and cold filter plugging point (CFPP), according to EN 14214 standard. High methyl ester yield and fast reaction rates were obtained in short reaction times. Ultrasound power and catalyst concentration had a positive effect on the yield and the reaction rate. The methanol:oil molar ratio also increased the yield of the reaction, but negatively influenced the process rate. The reaction followed a pseudo-first order kinetic model and the rate constants at several temperatures were determined. The activation energy was also determined using the Arrhenius equation. The main conclusion of this work is that the use of ultrasound irradiation did not require any additional heating, which could represent an energy savings for biodiesel manufacture.

Author(s):  
Elsy Arenas ◽  
Aidin Urribarrí ◽  
John Sánchez ◽  
Marisela Rincón ◽  
Karina Martínez ◽  
...  

Large quantities of used vegetable oils (AVUs) are generated annually, as a result of food preparation, which can cause contamination of waters and soils, if they are not disposed of properly, but in turn have great potential in the production of biodiesel. In this work, the AVU collected from fast food establishments were subjected to an esterification pretreatment, varying the reaction conditions, molar ratio, catalyst concentration and time, to decrease the content of free fatty acids generated in the frying processes; after an alkaline transesterification. The initial acidity of the AVUs (10,08 ± 0,22 %) was found to drop below 1 % during esterification at 60 °C and 100 rpm, with RMAVU:MeOH of 1: 7 and HCl concentration of 0.3 % v/v, with a conversion of free fatty acids (FFA) to methyl esters of 94.48 and 98.61 % for reaction times of 4 and 6 hours, respectively. The previously esterified AVUs were subjected to a transesterification process with KOH as a catalyst in the presence of methanol, at 60 °C and 100 rpm, finding that the biodiesel produced was a mixture composed of the methyl esters of linoleic acids (57 %), palmitic (14 %), oleic (22 %), stearic (4 %) and elaidic (3 %). The highest concentration of methyl esters (93,797 ± 0.685 g.L-1) was obtained when using the esterified AVU during 6 hours of reaction. FTIR spectra confirmed the conversion of fatty acids to methyl esters, so this product could be used as a biofuel.


2011 ◽  
Vol 11 (1) ◽  
pp. 41 ◽  
Author(s):  
Susan A Roces ◽  
Raymond Tan ◽  
Francisco Jose T Da Cruz ◽  
Shuren C Gong ◽  
Rison K Veracruz

Studies were carried out on the transesterification, also called methanolysis, of oil from the Jatropha curcas L. with methanol using conventional heating for the production of biodiesel. All reactions were carried out in a batch-stirred reactor and in the subsequent separation and purification stages. The high free-fatty acid (FFA) level of Jatropha oil was reduced to less than 1% by a two-step process. The first step was carried out with 12% w/w methanol-to-oil ratio in the presence of 1% w/w HCl as acid catalyst in a 2h reaction at 343K. The second step was carried out with variable parameters: temperatures at 318K and 333K, initial catalyst concentrations at 0.5% and 1.5%, methanol:oil molar ratios at 4:1 and 6:1, and reaction times at 1h and 2h. Gas chromatography analysis was used to determine the fatty acid profile of crude Jatropha oil. Methanolysis of Jatropha oil used the catalysts NaOH and KOH. The high FFA level of Jatropha oil was reduced from 6.1% to 0.7% after the first step process. The highest yield of fatty acid methyl esters (FAME), however, was achieved at 92.7% in 2h at 4:1 methanol:oil molar ratio, 1.5% w/w KOH, and 333K reaction temperature. This method produced biodiesel that met ASTM’s biodiesel standards. Results showed a density of 0.8g/ml that is within 0.86–0.9kg/l standard range and a kinematic viscosity of about 4.1cSt that is within 2–4.5cSt standard range. The flash point of the biodiesel samples fell between 169oC and 179oC while the cloud point averaged at 6oC.


Author(s):  
Muh. Irwan ◽  
Hamdani Saidi ◽  
M. A. Rachman ◽  
Ramli Ramli ◽  
Marlinda Marlinda

The biodiesel synthesis through alcoholysis process of triglyceride from Jatropha curcas using different type of alcohol, such as: methanol, ethanol, isopropyl alcohol and tert-butanol, was conducted in the presence of potassium hydroxide (KOH) as catalyst under 35 kHz frequency ultrasound irradiation. The optimum conditions, such as: alcohol to jatropha oil molar ratio, concentration of catalyst, reaction temperature, and reaction time, were found  to be 7:1 of alcohol to jatropha oil molar ratio, 0.5 % of KOH, temperature of reaction at 35 0C, within the reaction times of 15 minutes. The results obtained for the different types of alcohol were 62.77 %, 57.93 %, 51.64 %, and 46.77 % for methanol, ethanol, isopropyl alcohol, and tert-butanol, respectively. Copyright © 2017 BCREC Group. All rights reservedReceived: 11st November 2016; Revised: 8th March 2017; Accepted: 9th March 2017; Available online: 27th October 2017; Published regularly: December 2017How to Cite: Irwan, M., Saidi, H., Rachman, M.A., Ramli, R., Marlinda, M. (2017). Rapid Alcoholysis of Jatropha Curcas Oil for Biodiesel Production Using Ultrasound Irradiation. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (3): 306-311 (doi:10.9767/bcrec.12.3.801.306-311) 


Transport ◽  
2018 ◽  
Vol 33 (5) ◽  
pp. 1155-1161
Author(s):  
Eglė Sendžikienė ◽  
Violeta Makarevičienė ◽  
Kiril Kazancev

Some of the more recent methods of obtaining biodiesel are based on heterogeneous catalysis, which has the advantage of multiple uses of a catalyst. Natural minerals, such as dolomite, opoca and serpentinites, could be promising for use in biodiesel synthesis. The purpose of this study was to optimise the reaction conditions for biodiesel synthesis from sunflower oil and methanol using dolomite as a catalyst. Optimum reaction conditions for the transesterification of sunflower oil with methanol, using dolomite calcined at the temperature of 850 °C, have been identified: the amount of the catalyst – 6%, the molar ratio of methanol to oil – 8:1, the reaction duration – 5 hours and the reaction temperature – 60 °C. The amount of Fatty Acid Methyl Esters (FAME) of the sunflower oil obtained – 97.6%. FAME is in conformity with the EN 14214:2003 standard, when 500 ppm of antioxidant Ionol and 500 ppm of depressant Infineum R-442 are added. The Cold Filter Plugging Point (CFPP) of FAME is reduced to7 °C by adding 500 ppm of Infineum R-442. This product can be used in summer in the countries that are placed in Class E, including Lithuania. It has been established that dolomite without regeneration can be used for the transesterification of sunflower oil 2 times.


Processes ◽  
2021 ◽  
Vol 10 (1) ◽  
pp. 39
Author(s):  
Meiga Putri Wahyu Hardhianti ◽  
Rochmadi ◽  
Muhammad Mufti Azis

Esterification of rosin with pentaerythritol produces rosin pentaerythritol ester (RPE) which is widely used in paint, coating, and pressure-sensitive and hot-melt adhesive industries. Although RPE has excellent valuable applications and has been industrially produced, studies on the reaction kinetics have not been widely reported in the present literature. This work proposed a kinetic study of RPE synthesis by including a series of consecutive reactions forming mono-, di-, tri-, and tetra-ester with decarboxylation of rosin as a side reaction in the kinetics model. For esterification, the reaction rates were determined by the second-order kinetic model. The first-order kinetic order was proposed for decarboxylation. Kinetic experiments were performed at a temperature range of 260 °C to 290 °C. The initial molar ratio of pentaerythritol to rosin (in the mole of OH/COOH) used was between 0.8 and 1.2. A small amount of samples were withdrawn in certain time interval. The sample was analyzed to evaluate their acid and saponification number. Afterward, those experimental data were used to simulate and validate the proposed kinetic model. In general, the proposed model could capture the experimental data well. The resulting activation energies ranged from 65.81 to 129.13 kJ mol−1 for esterification and 233.00 kJ mol−1 for decarboxylation. This model also offers a new insight that correlates well with tetra-ester formation and the softening point.


2019 ◽  
Author(s):  
Chem Int

Biodiesel produced by transesterification process from vegetable oils or animal fats is viewed as a promising renewable energy source. Now a day’s diminishing of petroleum reserves in the ground and increasing environmental pollution prevention and regulations have made searching for renewable oxygenated energy sources from biomasses. Biodiesel is non-toxic, renewable, biodegradable, environmentally benign, energy efficient and diesel substituent fuel used in diesel engine which contributes minimal amount of global warming gases such as CO, CO2, SO2, NOX, unburned hydrocarbons, and particulate matters. The chemical composition of the biodiesel was examined by help of GC-MS and five fatty acid methyl esters such as methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linoleneate were identified. The variables that affect the amount of biodiesel such as methanol/oil molar ratio, mass weight of catalyst and temperature were studied. In addition to this the physicochemical properties of the biodiesel such as (density, kinematic viscosity, iodine value high heating value, flash point, acidic value, saponification value, carbon residue, peroxide value and ester content) were determined and its corresponding values were 87 Kg/m3, 5.63 Mm2/s, 39.56 g I/100g oil, 42.22 MJ/Kg, 132oC, 0.12 mgKOH/g, 209.72 mgKOH/g, 0.04%wt, 12.63 meq/kg, and 92.67 wt% respectively. The results of the present study showed that all physicochemical properties lie within the ASTM and EN biodiesel standards. Therefore, mango seed oil methyl ester could be used as an alternative to diesel engine.


1997 ◽  
Vol 32 (1) ◽  
pp. 101-118 ◽  
Author(s):  
Q.J. ROCHFORT ◽  
W.E. Watt ◽  
J. Marsalek ◽  
B.C. Anderson ◽  
A.A. Crowder

Abstract Two subsurface flow constructed wetlands were tested for pollutant removal performance in conjunction with an on-line stormwater detention pond, in Kingston Township, Ontario. The 4.9 m2 wetland cells were filled with 9 mm limestone gravel, and planted with cattail, common reed and spike rush. Changes in nutrient (total organic carbon, PO43- and NH4+), suspended solids and metal (Cu, Pb, Zn) concentrations were used to assess performance. Contaminant removal occurred through a combination of physical, chemical and biological means. As with any biological system, variation in performance of stormwater wetlands can be expected to occur as a result of fluctuations in contaminant loading, contact time and ambient environmental conditions. Storm pond effluent was delivered in continuous flow through the wetlands (during baseflow and event conditions), with a detention time of 1 to 3 days. The wetlands were able to maintain removal rates of up to 39% for orthophosphate even during the more severe conditions of fall dieback. Average removal of suspended solids (46%) and dissolved metals (Cu 50%) remained similar throughout all tests. Organic carbon was reduced by less than 10% during these tests. Low nutrient levels in the pond effluent were supplemented by spiking with sources of carbon, nitrogen and phosphorus during pulsed loading conditions. Daily sampling produced a time series, which illustrated the rates of decline in concentration of nutrients. First order kinetic assimilation rates ranged from 1.7 d-1 for NH4002B to 0.12 d-1 for organic carbon, which were noticeably lower when compared with municipal and industrial wastewater treatment rates. Three methods of sizing stormwater wetlands (impervious surface area, volumetric load and kinetic reaction rates) were compared using the same design storm and data from this study. From this comparison it was seen that the kinetic sizing approach proved to be the most versatile, and allowed for adaptation to northern climatic conditions and anticipated nutrient loading.


2018 ◽  
Vol 9 (1) ◽  
pp. 133-139
Author(s):  
Waleed S. Mohammed ◽  
Ahmed H. El-Shazly ◽  
Marwa F. Elkady ◽  
Masahiro Ohshima

Introduction: The utilization of biodiesel as an alternative fuel is turning out to be progressively famous these days because of worldwide energy deficiency. The enthusiasm for utilizing Jatropha as a non-edible oil feedstock is quickly developing. The performance of the base catalyzed methanolysis reaction could be improved by a continuous process through a microreactor in view of the high mass transfer coefficient of this technique. Materials & Methods: Nanozirconium tungstovanadate, which was synthetized using sol-gel preparation method, was utilized in a complementary step for biodiesel production process. The prepared material has an average diameter of 0.066 &µm. Results: First, the NaOH catalyzed methanolysis of Jatropha oil was investigated in a continuous microreactor, and the efficient mixing over different mixers and its impact on the biodiesel yield were studied under varied conditions. Second, the effect of adding the nanocatalyst as a second stage was investigated. Conclusion: The maximum percentage of produced methyl esters from Jatropha oil was 98.1% using a methanol/Jatropha oil molar ratio of 11 within 94 s using 1% NaOH at 60 &°C. The same maximum conversion ratio was recorded with the nanocatalyst via only 0.3% NaOH.


Energies ◽  
2020 ◽  
Vol 13 (22) ◽  
pp. 5868
Author(s):  
Jason Graetz ◽  
John J. Vajo

An investigation of electrolyte-assisted hydrogen storage reactions in complex aluminum hydrides (LiAlH4 and NaAlH4) reveals significantly reduced reaction times for hydrogen desorption and uptake in the presence of an electrolyte. LiAlH4 evolves ~7.8 wt% H2 over ~3 h in the presence of a Li-KBH4 eutectic at 130 °C compared to ~25 h for the same material without the electrolyte. Similarly, NaAlH4 exhibits 4.8 wt% H2 evolution over ~4 h in the presence of a diglyme electrolyte at 150 °C compared to 4.4 wt% in ~15 h for the same material without the electrolyte. These reduced reaction times are composed of two effects, an increase in reaction rates and a change in the reaction kinetics. While typical solid state dehydrogenation reactions exhibit kinetics with rates that continuously decrease with the extent of reaction, we find that the addition of an electrolyte results in rates that are relatively constant over the full desorption window. Fitting the kinetics to an Avrami-Erofe’ev model supports these observations. The desorption rate coefficients increase in the presence of an electrolyte, suggesting an increase in the velocities of the reactant-product interfaces. In addition, including an electrolyte increases the growth parameters, primarily for the second desorption steps, resulting in the observed relatively constant reaction rates. Similar effects occur upon hydrogen uptake in NaH/Al where the presence of an electrolyte enables hydrogenation under more practical low temperature (75 °C) and pressure (50 bar H2) conditions.


Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1583
Author(s):  
Natalia Guerrero-Alburquerque ◽  
Shanyu Zhao ◽  
Daniel Rentsch ◽  
Matthias M. Koebel ◽  
Marco Lattuada ◽  
...  

Ureido-functionalized compounds play an indispensable role in important biochemical processes, as well as chemical synthesis and production. Isocyanates, and KOCN in particular, are the preferred reagents for the ureido functionalization of amine-bearing compounds. In this study, we evaluate the potential of urea as a reagent to graft ureido groups onto amines at relatively low temperatures (<100 °C) in aqueous media. Urea is an inexpensive, non-toxic and biocompatible potential alternative to KOCN for ureido functionalization. From as early as 1864, urea was the go-to reagent for polyurea polycondensation, before falling into disuse after the advent of isocyanate chemistry. We systematically re-investigate the advantages and disadvantages of urea for amine transamidation. High ureido-functionalization conversion was obtained for a wide range of substrates, including primary and secondary amines and amino acids. Reaction times are nearly independent of substrate and pH, but excess urea is required for practically feasible reaction rates. Near full conversion of amines into ureido can be achieved within 10 h at 90 °C and within 24 h at 80 °C, and much slower reaction rates were determined at lower temperatures. The importance of the urea/amine ratio and the temperature dependence of the reaction rates indicate that urea decomposition into an isocyanic acid or a carbamate intermediate is the rate-limiting step. The presence of water leads to a modest increase in reaction rates, but the full conversion of amino groups into ureido groups is also possible in the absence of water in neat alcohol, consistent with a reaction mechanism mediated by an isocyanic acid intermediate (where the water assists in the proton transfer). Hence, the reaction with urea avoids the use of toxic isocyanate reagents by in situ generation of the reactive isocyanate intermediate, but the requirement to separate the excess urea from the reaction product remains a major disadvantage.


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