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- On the storage stability of CaO biodiesel catalyst: hydration and carbonation poisoningPublication . Soares Dias, A. P.; Ramos, MartaLime based catalysts are reported to be active in oil alcoholysis, biodiesel production, but their sensitivity to moisture and atmospheric CO2 can hinder their use at the industrial level because it is suspected that they must be manipulated in a controlled atmosphere. The storage stability of lime catalyst was investigated for 180 days (temperature in the range 20-38 degrees C, relative humidity higher than 40%). Catalytic data showed biodiesel yields ranging from 87.5%, for the first day, to 79.4% for the 180th day, passing through a maximum of 91.5% obtained in the 30th day of storage. Hydration was mainly a surface process since the Ca(OH)(2) bulk phase was detected only at the end of the storage period. A catalyst stored for 10 mounts was successfully reactivated by annealing at 470 degrees C thus proving that CaO material is stable enough during storage and handling to be used as a biodiesel catalyst.
- Solvent assisted biodiesel production by co-processing beef tallow and soybean oil over calcium catalystsPublication . Dias, Ana Paula Soares; Ramos, Marta; Catarino, Mónica Inês; Puna, Jaime; Gomes, JoãoDue 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.
- Biodiesel production processes and sustainable raw materialsPublication . Ramos, Marta; Dias, Ana; Puna, Jaime; Gomes, João; Bordado, JoãoEnergy security and environmental concerns, related to the increasing carbon emissions, have prompted in the last years the search for renewable and sustainable fuels. Biodiesel, a mixture of fatty acids alkyl esters shows properties, which make it a feasible substitute for fossil diesel. Biodiesel can be produced using different processes and different raw materials. The most common, first generation, biodiesel is produced by methanolysis of vegetable oils using basic or acid homogeneous catalysts. The use of vegetable oils for biodiesel production raises serious questions about biodiesel sustainability. Used cooking oils and animal fats can replace the vegetable oils in biodiesel production thus allowing to produce a more sustainable biofuel. Moreover, methanol can be replaced by ethanol being totally renewable since it can be produced by biomass fermentation. The substitution of homogeneous catalyzed processes, nowadays used in the biodiesel industry, by heterogeneous ones can contribute to improve the biodiesel sustainability with simultaneous cost reduction. From the existing literature on biodiesel production, it stands out that several strategies can be adopted to improve the sustainability of biodiesel. A literature review is presented to underline the strategies allowing to improve the biodiesel sustainability.
- The role of alkali dopants on the oil methanolysis behavior of lime catalyst: activity & stabilityPublication . Soares Dias, A. P.; Puna, Jaime; Gomes, João; Ramos, Marta; Rijo, Bruna; Bordado, JoãoHeterogeneous basic catalysts, namely calcium oxide, are referred to as promising catalysts for biodiesel (FAME, fatty acid methyl esters) production since they can be easily separated from the reaction medium allowing them to operate in a continuous mode. Despite the relatively high catalytic activity of calcium catalysts, they present slower alcoholysis rates than homogeneous conventional catalysts (sodium or potassium methanoate). In order to improve the catalytic activity, CaO-based catalysts, modified with alkali elements (Li, Cs, Sr, and Mg) were prepared. Dopant element contents of 10% and 30%, as weight basis (5–50% molar), were introduced by wet impregnation using aqueous solutions of nitrate salts. The effect of calcination temperature (575°C and 800°C) on both activity and stability was studied. All the prepared catalysts, raw and alkali modified, showed pKa<15.0 when characterized by Hammett indicators in methanolic solution. Such basicity is characteristic of Ca hydroxide, thus indicating that the catalysts surfaces were covered with Ca-OH species. FAME yield, in soybean oil methanolysis, higher than 96% was obtained for the first batch reaction for all the tested catalysts showing that alkali dopants have an almost nihil effect on the catalysts performances. The deactivation tests performed with catalysts without intermediate reactivation showed that calcination temperature plays a major role in stability as it enhances the formation of calcium diglyceroxide. The presence of Ca hydroxide in fresh catalysts appears to be responsible for fast deactivation. The dopant elements prompt the catalysts deactivation. Catalysts calcined at higher temperatures showed slower deactivation, which can be due to the formation of larger particles, thus reducing the contact with the formed glycerin. Alkali dopants enhanced the CaO sintering for the highest calcination temperature. Calcium diglyceroxide formed during the reaction is responsible for deactivating the catalyst, due to leaching, and such effect is prompted by alkali dopants.
- Catalyzed pyrolysis of coffee and tea wastesPublication . Rijo, Bruna; Soares Dias, A. P.; Ramos, Marta; Jesus, Nicole de; Puna, JaimeThe pyrolysis of food waste has a double environmental advantage as it contributes to the management and treatment of waste and allows the production of renewable fuels. Spent coffee and tea grounds, were characterized by thermogravimetry to determine their composition and evaluating the pyrolysis kinetics of each lignocellulosic pseudocomponent and pyrolyzed in a fixed bed reactor. Tea grounds had about twice the cellulose and higher pyrolysis activation energy than the coffee grounds sample. At 673 K the pyrolysis of the coffee grounds led to a 42% bio-oil yield while the tea grounds produced only 18% of liquid product, which is compatible with its higher cellulose content and the higher activation energy for pyrolysis. The alkaline carbonates used as pyrolysis catalysts led to an increase in the production of a gaseous product, bio-gas, with a reduction in the production of bio-oil but accompanied by a significant increase in the volatile fraction of the produced bio-oils. Pyrolysis data shows that both coffee and tea residues can be used as raw materials to produce pyrolysis bio-oil and that low-value materials such as alkaline carbonates can be used as pyrolysis catalysts improving the characteristics of bio-oils produced such as acidity and volatility.