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- Preliminary study on the use of biodiesel obtained from waste vegetable oils for blending with hydrotreated kerosene fossil fuel using Calcium Oxide (CaO) from natural waste materials as heterogeneous catalystPublication . Ozkan, Sila; Puna, Jaime; Gomes, João; Cabrita, T.; Palmeira, José; Santos, Maria TeresaIn this experimental work, calcium from natural seafood wastes was used as a heterogeneous catalyst separately or in a blend of "shell mix" for producing biodiesel. Several chemical reaction runs were conducted at varied reaction times ranging from 30 min to 8 h, at 60 degrees C, with a mass content of 5% (W-cat./W-oil) and a methanol/oil molar ratio of 12. After the purification process, the biodiesel with fatty acid methyl ester (FAME) weight content measured was higher than 99%, which indicated that it was a pure biodiesel. This work also showed that the inorganic solid waste shell mixture used as the heterogeneous catalyst can be reused three times and the reused mixture still resulted in a FAME content higher than 99%. After 40 different transesterification reactions were performed using liquid (waste cooking oils) and solid (calcium seafood shells) wastes for producing biodiesel, under the specific conditions stated above, we found a successful, innovative, and promising way to produce biodiesel. In addition, blends prepared with jet fuel A1 and biodiesel were recorded with no invalid results after certain tests, at 25 degrees C. In this case, except for the 10% blend, the added biodiesel had no significant effect on the viscosity (fluidity) of the biojet fuel.
- Study on the use of MgAl hydrotalcites as solid heterogeneous catalysts for biodiesel productionPublication . Gomes, João; Puna, Jaime; Gonçalves, Lissa M.; Bordado, JoãoThis paper, reports experimental work on the use of new heterogeneous solid basic catalysts for biodiesel production: double oxides of Mg and Al, produced by calcination, at high temperature, of MgAl lamellar structures, the hydrotalcites (HT). The most suitable catalyst system studied are hydrotalcite Mg:Al 2:1 calcinated at 507 degrees C and 700 degrees C, leading to higher values of FAME also in the second reaction stage. One of the prepared catalysts resulted in 97.1% Fatty acids methyl esters (FAME) in the 1st reaction step, 92.2% FAME in the 2nd reaction step and 34% FAME in the 3rd reaction step. The biodiesel obtained in the transesterification reaction showed composition and quality parameters within the limits specified by the European Standard EN 14214. 2.5% wt catalyst/oil and a molar ratio methanol:oil of 9:1 or 12:1 at 60 -65 degrees C and 4 h of reaction time are the best operating conditions achieved in this study. This study showed the potential of Mg/Al hydrotalcites as heterogeneous catalysts for biodiesel production. (C) 2011 Elsevier Ltd. All rights reserved.
- Calcium diglyceroxide as a catalyst for biodiesel productionPublication . Catarino, Mónica Inês; Martins, Susana; Ana Paula Soares Dias; Pereira, Manuel; Gomes, JoãoCalcium diglyceroxide (CaD) was used as the catalyst for biodiesel production through oil methanolysis. It was evaluated its catalytic behavior, its air expo- sure tolerance, and the Ca leaching. CaD catalyst was synthesized from food waste scallop shell derived CaO (obtained by calcination at 900 degrees C) by contacting with a mixture of equal volumes of glycerin and methanol at 65 degrees C for 2 h. The CaO obtained by calcination of scallop shell was used as reference catalyst. In standard reaction conditions (2.5 h, methanol reflux temperature, 5 wt% (oil basis) catalyst loading, and methanol: oil = 12:1 moral ratio), CaD presented lower catalytic activity than CaO (FAME yield of 92% against 99%, respectively). 24 h repined CaD presented improved catalytic behavior probably due to the formation of surface Ca - OH groups, achieving 96% of FAME yield. Thermogravimetry (TG) data showed that inorganic residue was larger for biodiesel than for glycerin, being CaD catalyst more soluble than CaO. Data showed that CaD is unstable under reaction conditions, suffering leaching, but the absence of Matter Organic Non-Glycerol (MONG) in the glycerin phase allows to neglect the homogeneous contribution of the leached catalyst. CaD formation during reaction contributes to FAME contamination with Ca and promotes catalyst deactivation thus being an undesired occurrence.
- Biodiesel production from waste frying oils over lime catalystsPublication . Puna, Jaime; Correia, Maria Joana Neiva; Dias, Ana Paula Soares; Gomes, João; Bordado, JoãoBiodiesel production from semi-refined oils (SRO) and waste frying oils (WFO) was studied using commercial CaO as heterogeneous catalyst. The methanolysis tests were carried out in mild reaction conditions (62 A degrees C, atmospheric pressure). With such conditions, SRO (soybean and rapeseed) allowed to produce a biodiesel containing 97-98 % of methyl esters (FAME), whereas WFO only provided 86-87 % of FAME. The lower FAME yield for WFO oil is ascribable to the partial neutralization of the catalyst by free fatty acids. Also, soaps formation from the WFO oil reduced the weight yield of the oil phase (containing FAME) obtained and increased the MONG content of the glycerin phase. The catalysts stability tests showed high stability even when WFO oil was processed. Catalytic tests performed with blends of WFO/semi-refined oils showed blending as a good strategy to process low value raw oils with minor decay of the catalyst performance. Both WFO and semi-refined oils showed S-shape kinetics curves thus discarding significant differences of the reaction mechanisms.
- Soybean oil transesterification for biodiesel production with micro-structured calcium oxide (CaO) from natural waste materials as a heterogeneous catalystPublication . Santos, Samuel; Nobre; Gomes, João; Puna, Jaime; Quinta-Ferreira, Rosa; J.C. Bordado, J. Moura Bordado, J.C.M. BordadoIn this study, micro-structured calcium oxide obtained from the calcination (850 degrees 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.
- Advances on the development of novel heterogeneous catalysts for transesterification of triglycerides in biodieselPublication . Puna, Jaime; Gomes, João; Correia, M. Joana N.; Dias, A. P. Soares; Bordado, J. C.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.