Abstract: The combination of world population and the third industrial revolution led to high demand for fuels. On the other hand, the decrease of global fossil 8fuels deposits and the environmental air pollution caused by these fuels has compounded the challenges the world faces due to its need for energy. Therefore, new forms of environmentally friendly and renewable fuels such as biodiesel are needed. The primary analytical techniques for methanolysis yield monitoring have been chromatography and spectroscopy, these methods have been proven reliable but are more demanding, costly and do not provide real-time monitoring. In this work, the in situ monitoring of biodiesel from sunflower oil using FTIR (Fourier Transform Infrared) has been studied; the study was performed using EasyMax Mettler Toledo reactor equipped with a DiComp (Diamond) probe. The quantitative monitoring of methanolysis was performed by building a quantitative model with multivariate calibration using iC Quant module from iC IR 7.0 software. 15 samples of known concentrations were used for the modelling which were taken in duplicate for model calibration and cross-validation, data were pre-processed using mean centering and variance scale, spectrum math square root and solvent subtraction. These pre-processing methods improved the performance indexes from 7.98 to 0.0096, 11.2 to 3.41, 6.32 to 2.72, 0.9416 to 0.9999, RMSEC, RMSECV, RMSEP and R2Cum, respectively. The R2 value of 1 (training), 0.9918 (test), 0.9946 (cross-validation) indicated the fitness of the model built. The model was tested against univariate model; small discrepancies were observed at low concentration due to unmodelled intermediates but were quite close at concentrations above 18%. The software eliminated the complexity of the Partial Least Square (PLS) chemometrics. It was concluded that the model obtained could be used to monitor methanol of sunflower oil at industrial and lab scale.
Abstract: The current study investigated the effect of catalyst ratio and methanol to oil ratio on biodiesel production by using central composite design. Biodiesel was produced by transesterification using sodium hydroxide as a homogeneous catalyst, a laboratory scale reactor consisting of flat bottom flask mounts with a reflux condenser, and a heating plate was used to produce biodiesel. Key parameters, including time, temperature, and mixing rate was kept constant at 60 minutes, 60 oC and 600 RPM, respectively. From the results obtained, it was observed that the biodiesel yield depends on catalyst ratio and methanol to oil ratio. The highest yield of 50.65% was obtained at catalyst ratio of 0.5 wt.% and methanol to oil mole ratio 10.5. The analysis of variances of biodiesel yield showed the R Squared value of 0.8387. A quadratic mathematical model was developed to predict the biodiesel yield in the specified parameters ranges.
Abstract: Grape seeds are waste products of wineries and often referred to as an important agricultural and industrial waste product with the potential to be used in pharmaceutical, food, and cosmetic applications. In this study, grape seed oil from traditional Ionian varieties was examined for the determination of the quality and the characteristics of each variety. Initially, the fatty acid methyl ester (FAME) profiles were analyzed using Gas Chromatography-Mass Spectrometry, after transesterification. Furthermore, other quality parameters of the grape seed oils were determined by Spectroscopy techniques, UV-Vis and Raman included. Moreover, the antioxidant capacity of the oil was measured by 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assays and their antioxidant capacity expressed in Trolox equivalents. K and ΔΚ indices were measured in 232, 268, 270 nm, as an oil quality index. The results indicate that the air-dried grape seed total oil content ranged from 5.26 to 8.77% w/w, which is in accordance with the other grape seed varieties tested in similar studies. The composition of grape seed oil is predominated with linoleic and oleic fatty acids, with the linoleic fatty acid ranging from 53.68 to 69.95% and both the linoleic and oleic fatty acids totaling 78-82% of FAMEs, which is analogous to the fatty acid composition of safflower oil. The antioxidant assays ABTS and DPPH scored high, exhibiting that the oils have potential in the cosmetic and culinary businesses. Above that, our results demonstrate that Ionian grape seed oils have prospects that can go further than cosmetic or culinary use, into the pharmaceuticals industry. Finally, the reclamation of grape seeds from wineries waste stream is in accordance with the bio-economy strategic framework and contributes to environmental protection.
Abstract: The current study investigated the effect of catalyst ratio and methanol to oil ratio on biodiesel production by using central composite design. Biodiesel was produced by transesterification using sodium hydroxide as a homogeneous catalyst, a laboratory scale reactor consisting of flat bottom flask mounts with a reflux condenser and a heating plate was used to produce biodiesel. Key parameters, including, time, temperature and mixing rate were kept constant at 60 minutes, 60 oC and 600 RPM, respectively. From the results obtained, it was observed that the biodiesel yield depends on catalyst ratio and methanol to oil ratio. The highest yield of 50.65% was obtained at catalyst ratio of 0.5 wt.% and methanol to oil mole ratio 10.5. The analysis of variances of biodiesel yield showed the R Squared value of 0.8387. A quadratic mathematical model was developed to predict the biodiesel yield in the specified parameters ranges.
Abstract: Strong anion exchange resins with QN+OH-, have the
potential to be developed and employed as heterogeneous catalyst for
transesterification, as they are chemically stable to leaching of the
functional group. Nine different SIERs (SIER1-9) with QN+OH-were
prepared by suspension polymerization of vinylbenzyl chloridedivinylbenzene
(VBC-DVB) copolymers in the presence of n-heptane
(pore-forming agent). The amine group was successfully grafted into
the polymeric resin beads through functionalization with
trimethylamine. These SIERs are then used as a catalyst for the
transesterification of triacetin with methanol. A set of differential
equations that represents the Langmuir-Hinshelwood-Hougen-
Watson (LHHW) and Eley-Rideal (ER) models for the
transesterification reaction were developed. These kinetic models of
LHHW and ER were fitted to the experimental data. Overall, the
synthesized ion exchange resin-catalyzed reaction were welldescribed
by the Eley-Rideal model compared to LHHW models,
with sum of square error (SSE) of 0.742 and 0.996, respectively.
Abstract: Transesterification reactions free of catalyst between
roasted chicken fat with methanol were carried out in a batch reactor
in order to produce biodiesel to temperatures from 120°C to 140°C.
Parameters related to the transesterification reactions, including
temperature, time and the molar ratio of chicken fat to methanol also
investigated. The maximum yield of the reaction was of 98% under
conditions of 140°C, 4 h of reaction time and a molar ratio of chicken
fat to methanol of 1:31. The biodiesel thus obtained exhibited a
viscosity of 6.3 mm2/s and a density of 895.9 kg/m3. The results
showed this process can be right choice to produce biodiesel since
this process does not use any catalyst. Therefore, the steps of
neutralization and washing are avoided, indispensables in the case of
the alkaline catalysis.
Abstract: Commercially available lipases (Candida antarctica lipase B, Novozyme 435, Thermomyces lanuginosus lipase, and Lipozyme TL IM), as well as sol-gel immobilized lipases, have been screened for their ability to acylate regioselectively xylitol, sorbitol, and mannitol with a phenolic ester in a binary mixture of t-butanol and dimethylsulfoxide. HPLC and MALDI-TOF MS analysis revealed the exclusive formation of monoesters for all studied sugar alcohols. The lipases immobilized by the sol-gel entrapment method proved to be efficient catalysts, leading to high conversions (up to 60%) in the investigated acylation reactions. From a sequence of silane precursors with different nonhydrolyzable groups in their structure, the presence of octyl and i-butyl group was most beneficial for the catalytic activity of sol-gel entrapped lipases in the studied process.
Abstract: There is growing interest in biodiesel (fatty acid
methyl ester or FAME) because of the similarity in its properties
when compared to those of diesel fuels. Diesel engines operated on
biodiesel have lower emissions of carbon monoxide, unburned
hydrocarbons, particulate matter, and air toxics than when operated
on petroleum-based diesel fuel. Production of fatty acid methyl ester
(FAME) from rapeseed (nonedible oil) fatty acid distillate having
high free fatty acids (FFA) was investigated in this work. Conditions
for esterification process of rapeseed oil were 1.8 % H2SO4 as
catalyst, MeOH/oil of molar ratio 2 : 0.1 and reaction temperature
65 °C, for a period of 3h. The yield of methyl ester was > 90 % in 1
h.
The amount of FFA was reduced from 93 wt % to less than 2 wt %
at the end of the esterification process. The FAME was pureed by
neutralization with 1 M sodium hydroxide in water solution at a
reaction temperature of 62 °C. The final FAME product met with the
biodiesel quality standard, and ASTM D 6751.
Abstract: The conventional production of biodiesel from crude
palm oil which contains large amounts of free fatty acids in the
presence of a homogeneous base catalyst confronts the problems of
soap formation and very low yield of biodiesel. To overcome these
problems, free fatty acids must be esterified to their esters in the
presence of an acid catalyst prior to alkaline-catalyzed
transesterification. Sulfated metal oxides are a promising group of
catalysts due to their very high acidity. In this research, aluminadoped
sulfated tin oxide (SO4
2-/Al2O3-SnO2) catalysts were prepared
and used for esterification of free fatty acids in crude palm oil in a
batch reactor. The SO4
2-/Al2O3-SnO2 catalysts were prepared from
different Al precursors. The results showed that different Al
precursors gave different activities of the SO4
2-/Al2O3-SnO2 catalysts.
The esterification of free fatty acids in crude palm oil with methanol
in the presence of SO4
2-/Al2O3-SnO2 catalysts followed first-order
kinetics.