• Energy Research

Biodiesel produced by alcoholysis of vegetable oils is a low carbon fuel, which can replace the fossil diesel in internal combustion engines. CaO is a cheap and environmentally benign material showing interesting catalytic performances in the methanolysis reaction of vegetable oils. However, the reaction rate is slower than the conventional homogeneous-catalyzed by sodium methoxide. In order to improve the catalytic activity, lime catalyst (commercial) was doped with different amounts of strontium. The catalysts, prepared by wet impregnation using aqueous solutions of nitrate salt, were calcined at 575 °C and 800 °C. The physical-chemical characterization of catalysts showed that the doping element had an apparently null effect on the basicity assessed by Hammett indicators. The Ca(OH)2, with weak basicity, formed in the Sr-modified catalysts eventually masked the Sr effect on the basicity. In the tested conditions, all the prepared catalysts were active allowing fatty acid methyl esters’ (FAME) yields higher than 94%. The catalyst stability tests, performed without intermediate reactivation, showed that Sr dopant promoted accelerated decay due to calcium diglyceroxide formation which is leached into the reaction medium. High temperature calcination had a negative effect on the catalyst stability due to the formation of Ca(OH)2. Such undesired effect was prompted by the Sr dopant.

Due to sustainability issues, biodiesel must be produced from low-grade fats and the conventional homogeneously-catalyzed processes must be replaced by more efficient and more profitable production processes such as heterogeneous ones. Biodiesel (fatty acids methyl esters, FAME) was produced from a mixture (50 wt%) of soybean oil and non-edible beef tallow over heterogeneous calcium-based catalysts obtained by calcination of scallop shells. In order to improve the catalytic performances, solvent assisted methanolysis was conducted using alcohols (ethanol, 1-propanol, isopropanol and isobutanol), acetone, methylcyclohexane, and tetrahydrofuran (THF) with Vmethanol/Vsolvent = 2.8. Catalytic data revealed that alcohol solvents adsorb competitively with methanol on the catalyst active sites reducing the FAME yield due to their slower alcoholysis rates. Hexane and methylcyclohexane are inadequate for methanolysis reactions since they are immiscible with methanol. THF and acetone are immiscible with the co-produced glycerin, which favors methyl esters formation by displacing the chemical equilibrium towards reaction products. Acetone performs better than THF (FAME yield gain of 14% against 3%) because of its higher miscibility with methanol. THF was the most effective solvent to avoid fat adsorption on the catalyst surface, a key factor for catalyst stability, and to improve the glycerin purity.

Abstract Lime is pointed out as an effective catalyst for biodiesel production by oil methanolysis. Several Ca phases are formed during reaction. Each Ca phase has different contribution to the catalyzed process. Using CaO as a catalyst, S shape kinetics curve was observed and the induction period can be ascribed to the Ca(OH) 2 formation. When Ca(OH) 2 , prepared by contacting CaO with H 2 O, is used as catalyst the initial period with a slow rate of transesterification has almost vanished. Besides, if the catalyst surface is totally converted into methoxide species the induction period is longer than the analogous obtained with CaO. This is an indication that the methoxide species strongly bonded to Ca are less reactive. The calcium diglyceroxide material (CaO_diglyc), prepared by contacting CaO with a mixture of methanol and glycerol, displays a totally different kinetics curve with no induction period. The faster kinetics and the Ca species detected in the glycerin phase seem to underline a non-negligible homogeneous process contribution. The characterization of the post-reaction catalysts underlines the relevance of the surface and bulk catalyst modifications. Calcium hydroxide can be pointed out as the active phase whereas calcium diglyceroxide is responsible for the catalyst deactivation due to calcium leaching.

This study is focused on the modelling of the production of bio-oil by thermochemical liquefaction. Species Acacia melanoxylon was used as the source of biomass, the standard chemical 2-Ethylhexanol (2-EHEX) was used as solvent, p-Toluenesulfonic acid (pTSA) was used as the catalyst, and acetone was used for the washing process. This procedure consisted of a moderate acid-catalysed liquefaction process and was applied at 3 different temperatures to determine the proper model: 100, 135, and 170 °C, and at 30-, 115-, and 200-min periods with 0.5%, 5.25%, and 10% (m/m) catalyst concentrations of overall mass. Optimized results showed a bio-oil yield of 83.29% and an HHV of 34.31 MJ/kg. A central composite face-centred (CCF) design was applied to the liquefaction reaction optimization. Reaction time, reaction temperature, as well as catalyst concentration, were chosen as independent variables. The resulting model exhibited very good results, with a highly adjusted R-squared (1.000). The liquefied products and biochar samples were characterized by Fourier-transformed infrared (FTIR) and thermogravimetric analysis (TGA); scanning electron microscopy (SEM) was also performed. The results show that invasive species such as acacia may have very good potential to generate biofuels and utilize lignocellulosic biomass in different ways. Additionally, using acacia as feedstock for bio-oil liquefaction will allow the valorisation of woody biomass and prevent forest fires as well. Besides, this process may provide a chance to control the invasive species in the forests, reduce the effect of forest fires, and produce bio-oil as a renewable energy.

Biodiesel produced from food wastes can help to solve several environmental issues: anthropogenic carbon emissions due to fossil fuels combustion and waste management. Biodiesel was produced using waste frying oils (WFO) and calcium rich food wastes such as mollusk, shrimp, eggs shells and cuttlebone to produce calcium based heterogeneous catalysts by calcination. The characterization of chalky white calcined powders by XRD showed diffraction lines typical of lime but some samples were slightly contaminated with calcite. The powders with low crystallinity showed high hydration rate presenting XRD features ascribable to nanocrystals of calcium hydroxide. The post reaction samples presented mainly lines due to calcium diglyceroxide and methoxide. Thermograms of used catalysts showed some weight loss of these calcium compounds, confirming the presence of such phases. All prepared catalysts were effective in catalyzing the methanolysis of soybean oil. A FAME yield around 96% was obtained after 2.5 h of reaction. When using WFO, the FAME yield was only 65% with simultaneous production of soap. The use of WFO and soybean oil mixtures attenuates the loss of catalytic performances. The obtained glycerin’s presented a light color characteristic of heterogeneous catalyzed processes. FTIR spectra of glycerin’s showed some features belonging to matter organic non glycerin and methanol. The catalyst reutilization without intermediate reactivation indicated that catalysts are somewhat stable. When WFO was used, the reused catalysts showed improved performance probably due to the formation of calcium diglyceroxide. Nevertheless, calcium diglyceroxide is bound to promote homogeneous catalysis and consequent deactivation.

This paper describes experimental work done towards the search for more profitable and sustainable alternatives regarding biodiesel production, using heterogeneous catalysts instead of the conventional homogenous alkaline catalysts, such as NaOH, KOH or sodium methoxide, for the methanolysis reaction. This experimental work is a first stage on the development and optimization of new solid catalysts, able to produce biodiesel from vegetable oils. The heterogeneous catalytic process has many differences from the currently used in industry homogeneous process. The main advantage is that, it requires lower investment costs, since no need for separation steps of methanol/catalyst, biodiesel/catalyst and glycerine/catalyst. This work resulted in the selection of CaO and CaO modified with Li catalysts, which showed very good catalytic performances with high activity and stability. In fact FAME yields higher than 92% were observed in two consecutive reaction batches without expensive intermediate reactivation procedures. Therefore, those catalysts appear to be suitable for biodiesel production.

The continuous increase of the world’s population results in an increased demand for energy drastically from the industrial and domestic sectors as well. Moreover, the current public awareness regarding issues such as pollution and overuse of petroleum fuel has resulted in the development of research approaches concerning alternative renewable energy sources. Amongst the various options for renewable energies used in transportation systems, biodiesel is considered the most suitable replacement for fossil-based diesel. In what concerns the industrial application for biodiesel production, homogeneous catalysts such as sodium hydroxide, potassium hydroxide, sulfuric acid, and hydrochloric acid are usually selected, but their removal after reaction could prove to be rather complex and sometimes polluting, resulting in increases on the production costs. Therefore, there is an open field for research on new catalysts regarding biodiesel production, which can comprise heterogeneous catalysts. Apart from that, there are other alternatives to these chemical catalysts. Enzymatic catalysts have also been used in biodiesel production by employing lipases as biocatalysts. For economic reasons, and reusability and recycling, the lipases urged to be immobilized on suitable supports, thus the concept of heterogeneous biocatalysis comes in existence. Just like other heterogeneous catalytic materials, this one also presents similar issues with inefficiency and mass-transfer limitations. A solution to overcome the said limitations can be to consider the use of nanostructures to support enzyme immobilization, thus obtaining new heterogeneous biocatalysts. This review mainly focuses on the application of enzymatic catalysts as well as nano(bio)catalysts in transesterification reaction and their multiple methods of synthesis.

In this study, micro-structured calcium oxide obtained from the calcination (850 °C for 3 h) of Gallus gallus domesticus (chicken) eggshells was used as a catalyst in the transesterification of soybean oil. This catalyst was characterized by Scanning Electron Spectroscopy (SEM) methods. The structure of the obtained CaO showed several agglomerates of white granular solids with a non-regular and unsymmetrical shape. In terms of calcium oxide catalytic activity, three different catalyst loadings (1%wt, 3%wt, and 5%wt) were tested for the same reaction conditions, resulting in transesterification yields of 77.27%wt, 84.53%wt, and 85.83%wt respectively. The results were compared to the current literature, and whilst they were lower, they were promising, allowing us to conclude that the tendency of yield improvement for this reaction, when the size range of catalyst particles is to be reduced to a nano scale, can be verified.