Heterogenization of the biodiesel synthesis catalysis: CaO and novel calcium compounds as transesterification catalysts

Although CaO is one of the most studied basic heterogeneous catalysts for the synthesis of biodiesel, there are important issues that have been addressed by only a few research groups and that deserve further investigation. This is the case of the difficulties introduced by the poisoning of CaO upon exposure to ambient air and the role played by CaO-glycerol complexes on the catalytic performance. The purpose of this work is to provide new information on these issues in order to contribute to a better understanding of the underlying phenomena. Four commercial CaO samples have been considered to investigate their activation and stability under reaction conditions. In addition, calcium glyceroxide, and, for the first time, calcium glycerolate, have been synthesized and compared with the materials obtained from the commercial samples. The solids have been characterized with special emphasis on the assessment of their basic properties. The catalytic tests revealed big differences between the performance of the commercial solids that were substantially reduced after calcination and, specially, Ca-glyceroxide formation during reaction. Ca-glycerolate was the most resistant catalyst to ambient air although it was characterized by a low initial activity. Ca-glyceroxide could be reutilized for at least 5 reaction cycles without activity loss.     

Free lipase-catalyzed biodiesel production from phospholipids-containing oils

Free lipase-catalyzed biodiesel has drawn more and more attentions in recent years because of its advantages of lower cost and faster reaction rate. Utilizing free lipase to convert low quality oils such as crude vegetable oils and microbial oils is beneficial to further reduce the cost of biodiesel production. However, these oils typically contain some amount of phospholipids. Phospholipids were found to affect the lipase-catalyzed process and further influence the enzyme's thermal stability in biodiesel production process. In this work, free lipase NS81006-mediated biodiesel production from oils containing phospholipids at varied temperature was investigated systematically. It was found that the presence of phospholipids at high temperature led to a decreased fatty acid methyl esters (FAME) yield and poor reuse stability of the lipase during NS81006-catalyzed biodiesel production process. The higher the temperature was, the greater negative effect was observed. This inhibitory effect was found to be mainly caused by the coexistence of phospholipids and methanol in the system. Based on this finding, a novel two-step enzyme-mediated process was further developed, with which the above-mentioned inhibitory effect was eliminated, and a FAME yield of 95.1% could be obtained with oils containing 10% phospholipids even at high temperature of 55 °C.     

Sources of Methyl Ester Yield Reduction in Methanolysis of Recycled Vegetable Oil

Recycled vegetable oil (RVO) is a relatively cheap raw material for biodiesel production, but biodiesel grade methyl ester yields from RVO were found to be considerably lower than those from pure plant oil. The present paper investigates sources of yield loss during methanolysis of RVOs with free fatty acids (FFA) contents of 0.4–3.3%, and makes suggestions for the improvement of methyl ester yields. Data presented here indicated that yield losses of methyl esters during methanolysis were due to triglyceride and methyl ester hydrolysis and to the dissolution of methyl esters in the glycerol phase. Hydrolysis of triglycerides and methyl esters seemed to be the only side reaction causing yield losses, and the amount of fatty acids from hydrolysis increased with concentration of the potassium hydroxide catalyst. Dissolution of methyl esters in the glycerol phase was probably caused by the detergent effect of potassium salts of fatty acids originating from FFA in the RVO and from triglyceride hydrolysis, and the amount of dissolved methyl esters increased with FFA content of the RVO. The FFA content of the RVO had no effect on hydrolysis, and the amount of triglycerides and methyl esters hydrolysed during methanolysis remained constant with increasing FFA content of the RVO.     

A kinetic study of quicklime-catalyzed sunflower oil methanolysis

The quicklime-catalyzed sunflower oil methanolysis was studied at mild reaction conditions. Quicklime (calcined at 550 °C for 4 h) in amounts of 1.0, 2.5, 5.0 and 10.0% (based on the oil weight) and different molar ratios of methanol-to-oil (6:1, 12:1 and 18:1) were employed to investigate their influence on the methyl esters content and the kinetics of the methanolysis reaction. The optimal methanol-to-oil molar ratio and quicklime amount for achieving the highest fatty acid methyl esters content were established to be 12:1 and 5% (based on the oil weight), respectively. The sigmoidal kinetics of quicklime-catalyzed methanolysis reaction was described by a model which included the changing mechanism of the reaction and the triacylglycerols mass transfer limitation. The kinetic parameters were determined and correlated with the process variables. A good agreement between the kinetic model and the experimental data for all applied reaction conditions was observed.     

Methanolysis of ammonia borane catalyzed by magnetically isolable RHODIUM(0) nanoparticles

This article reports the preparation and employment of rhodium (0) nanoparticles (Rh⁰NPs) on the surface of magnetite nanospheres, denoted as Rh⁰@Fe₃O₄, as magnetically isolable nanocatalyst in the methanolysis of ammonia borane (MAB). The monodispersed Fe₃O₄ nanospheres are fabricated by a simple technique and used as nanosupport for Rh⁰NPs which are well stabilized and homogeneously distributed on the surface of nanospheres with a mean particle size of 2.8 ± 0.5 nm. The as-synthesized Rh⁰@Fe₃O₄ has a remarkable TOF value of 184 min⁻¹ in the MAB to produce H₂ gas in RT. Most of all, Rh⁰@Fe₃O₄ nanocatalyst can be reused, evolving 3.0 mol of H₂ gas for a mole of AB, keeping 100% of its initial activity even in the fourth reuse of MAB at 25 °C. Recovery of the Rh⁰@Fe₃O₄ nanocatalyst can be accomplished by simply approaching an external magnet, which eliminates many laborious catalyst removal steps in catalytic reactions. Reported are the outcomes of kinetic investigation, done by altering the concentration of substrate and catalyst together with temperature. Kinetic studies reveal that the catalytic MAB shows dependence on the concentration of reactants and temperature.     

A novel hazelnutt bagasse based activated carbon as sodium borohydride methanolysis and electrooxidation catalyst

In this study, activated carbon is produced from defatted hazelnut bagasse at different activation conditions. The catalytic activities of activated carbons are evaluated for NaBH₄ methanolysis and electrooxidation. These materials are characterized by N₂ adsorption-desorption, FTIR, SEM-EDS and XPS and results show that these materials are prepared successfully. N₂ adsorption-desorption results reveal that activated carbon (FH3-500) has the highest BET surface area as 548 m²/g, total pore volume as 0.367 cm³/g and micropore volume as 0.205 cm³/g. On the orher hand, as a result of hydrogen production studies, FH3-500 activated carbon catalyst has the highest initial hydrogen production rate compared to other materials. At 50 °C, this metal-free activated carbon catalyst has a high initial hydrogen production rate of 13591.20 mL/min.g_cat, which is higher than literature values. Sodium borohydride electrooxidation measurements reveal that FH2-500 also has the highest electrocatalytic activity and stability. Hazelnut pulp-based activated carbons are firstly used as a metal-free catalyst in the methanolysis and electrooxidation of sodium borohydride, and its catalytic activity is good as a metal-free catalyst. The results show that the hazelnut pulp-based activated carbon catalyst is promising as a metal-free catalyst for the methanolysis and electrooxidation of sodium borohydride.     

The preparation and performance of a novel spherical spider web-like structure RuNi / Ni foam catalyst for NaBH4 methanolysis

In this work, a spherical spider web-like structure RuNi/Ni foam catalyst was prepared for hydrogen evaluation from sodium borohydride (NaBH₄) by a combination of electroless plating and electroplating. Microstructure, surface morphology, surface area and elemental composition of the RuNi/Ni foam catalyst were analyzed by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM-EDS and X-ray Photoelectron Spectroscopy (XPS), Brunauere-Emmette-Teller method (BET, AS-1C-VP), respectively. The influences of RuNi with different molar ratios, NaOH concentration, NaBH₄ concentration, and solution temperature on the hydrogen production rate were investigated in this paper. The results showed that the RuNi metals were arrayed densely and uniformly on the surface of Ni foam. The average hydrogen production rate is 360 mL min ⁻¹ g⁻¹ in 20 wt % of NaBH₄, 1 wt% of NaOH at 30 °C in the presence of the RuNi/Ni foam catalysts. The calculated activation energy was 39.96 kJ mol⁻¹ for hydrogen production from sodium borohydride using the RuNi/Ni foam catalyst.     

Orange peel ash coated Fe3O4 nanoparticles as a magnetically retrievable catalyst for glycolysis and methanolysis of PET waste

Chemical recycling of PET offers the process of recovering virgin grade raw materials that can be reprocessed to produce an intact polymeric material or other valuable products. In the current study, we investigate the advantages of exercising biowaste derived orange peel ash (OPA) magnetic nano-catalyst, OPA@Fe₃O₄ as a green and reusable heterogeneous solid catalyst for glycolytic and methanolytic degradation of PET waste. The composition and physical features of the prepared catalyst were studied and analyzed using various techniques. Under the optimized condition, the catalyst was able to obtain an excellent bis(2-hydroxyethyl) terephthalate (BHET) and dimethyl terephthalate (DMT) yield with 100% PET conversion. Moreover, the catalyst was able to be recycled for ten consecutive runs for both processes without a significant reduction in the yield of the reaction, addressing the possible implementation of the catalyst for industrial purposes.