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Solid Acid Resin Amberlyst 45 as a Catalyst for the Transesterification of Vegetable Oil.

ABSTRACT: Commercial transesterification of vegetable oil to biodiesel using alkaline hydroxides requires expensive refined vegetable oil and anhydrous alcohols to avoid saponification. These issues are not present in the acid-catalyzed process; however, the challenge still lies in developing stable and active solid acid catalysts. Herein, Amberlyst 45, a resin for high-temperature application, was efficiently used for biodiesel production by the methanolysis or ethanolysis of vegetable oil. Yields of up to 80 and 84% were obtained for the fatty acid methyl ester and the fatty acid ethyl ester, respectively. Two processes are proposed and showed to be efficient: (i) incremental addition of alcohol along with the reaction for both methanolysis and ethanolysis; or (ii) one-pot reaction for ethanolysis using oil/ethanol molar ratio of 1/18. The catalytic system used also showed to be compatible with used oil (2.48 ± 0.03 mgNaOH goil-1 ) and to the presence of water (10-20 wt. % based on the alcohol), allowing the use of waste oil and hydrated alcohol.

SUBMITTER: Cabral NM

PROVIDER: S-EPMC7201088 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

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Solid Acid Resin Amberlyst 45 as a Catalyst for the Transesterification of Vegetable Oil.

Cabral Natalia Mariano NM Lorenti Juliana P JP Plass Winfried W Gallo Jean Marcel R JMR

Frontiers in chemistry 20200429

Commercial transesterification of vegetable oil to biodiesel using alkaline hydroxides requires expensive refined vegetable oil and anhydrous alcohols to avoid saponification. These issues are not present in the acid-catalyzed process; however, the challenge still lies in developing stable and active solid acid catalysts. Herein, Amberlyst 45, a resin for high-temperature application, was efficiently used for biodiesel production by the methanolysis or ethanolysis of vegetable oil. Yields of up ...[more]

PMID: 32411662

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Project description:The data employed the blend of waste used oil and beef tallow for the synthesis of fatty acid ethyl ester (FAEE) via ethanolysis of developed catalyst from calcined fermented cocoa pod husk powder (CFCPHP) doped with burnt cocoa pod husk powder (BCHP). Characterization of the developed doped catalyst (DDC) was carried out using FTIR, SEM, XRD, and BET adsorption analysis, while the basic strength of the DDC was tested through reusability test data. Mathematical optimization of the process condition was carried out through Box-Behnken Experimental Design (BBED) in 29 runs with variations in four variables as catalyst concentration (1.5 to 3.5 wt.%), reaction time (60 to 100 min), ethanol/oil molar ratio (EtOH/OMR) of 3 to 7, and reaction temperature (60 to 80 °C). The FAEE quality was ascertained by determining its fuel properties. The data showed that the binary blend ratio of 42:58 of Waste Used oil: Beef Tallow oil (WUO: BTO) was obtained through API gravity ratio formulation. The developed doped catalyst (DDC) produced a high CaO-base of 84.30 (wt.%), with a high total basic site of 210 μmole.g-1 via BET and XRD analysis. The SEM analysis dataset showed non-uniform sizes, highly porous and crystalline sample, while the dataset on FTIR analysis data confirmed the presence of wagging and twisting CO3 2-, the bending vibration of O-Ca-O, the sp2 of C = O, C = C, the sp of C  ≡  C and C  ≡  N, the bending structure of O-H, and the O=O, N ≡ O of Amines, and Amides. Based on the experiment, the maximum experimental yield of 97.80 (%wt.) at runs 7, and low yield of 89.50 (%wt.) at run 17 was obtained for FAEE. Mathematical optimization in 10 solutions predicted the FAEE yield of 97.7999 (%wt.) at the catalyst concentration of 3.10 (wt.%), the reaction time of 68.09 min, the EtOH/OMR of 3.01, and the reaction temperature of 72.21 °C. This data was validated in replicate, and the average mean value of FAEE was 97.68 (%wt.). Dataset on ANOVA and parametric analysis showed that the variable factors considered were significant at p-value <0.0001, with high R2 of 99.14%, R2-predicted of 98.32%, R2-adjusted of 98.28%, and adequate precision of 51.152, respectively. Catalyst reusability test data showed that the cycle number was stopped at the 5th cycle due to the decrease in catalyst basic strength. The produced FAEE dataset was within the recommended standard, and the data showed the developed doped catalyst successfully converted binary blend oil to FAEE, and the fermentation process increased the CaO-based conversion of DDC.

Project description:Differences in catalyst deactivation kinetics in solid acid catalysis are studied with catalyst models that allow for lateral interaction between protons. Deactivation of a solid acid catalyst with laterally interacting protons induces inhomogeneity of proton reactivity that develops with time. As a consequence, product selectivity changes and deactivation will accelerate. This is demonstrated by simulations of the deactivation kinetics of the alkylation reaction of propylene with isobutane. The effect of lateral interactions between protons arises because initial catalyst deactivation is not caused by pore blocking or coke deposition but by a molecular mechanism where protons are consumed due to the formation of stable nonreactive carbenium ions. High selectivity to alkylate requires a catalyst with protons of high reactivity. When protons become consumed by formation of stable deactivating carbenium ions, initially reactive protons are converted into protons of lower reactivity. The latter only catalyze deactivating oligomerization reactions. Simulations that compare the deactivation kinetics of a catalyst model with laterally interacting protons and a catalyst model that contains protons of similar but different reactivity, but that do not laterally interact, are compared. These simulations demonstrate that the lateral interaction catalyst model is initially more selective but also has a lower stability. Catalyst deactivation of the alkylation reaction occurs through two reaction channels. One reaction channel is due to oligomerization of reactant propylene. The other deactivation reaction channel is initiated by deprotonation of intermediate carbenium ions that increase alkene concentration. By consecutive reactions, this also leads to deactivation. The hydride transfer reaction competes with oligomerization reactions. It is favored by strongly acid sites that also suppress the deprotonation reaction. Within the laterally interacting proton catalyst model, when reactive protons become deactivated, weakly reactive protons are generated that only catalyze the deactivating alkene oligomerization and consecutive reactions. This rapid formation of the weakly reactive protons is the cause of decreasing selectivity with reaction time and increased rate of deactivation. Solutions of the mean field kinetic equations as well as stochastic simulations are presented. Comparative simulations with a reduced number of neighbors of the protons illustrate decreased deactivation rates when the proton density decreases. Island formation of adsorbed reaction intermediates on the catalyst surface is observed in stochastic kinetics simulations. When alkylation selectivity is high, this island formation increases the rate of catalyst deactivation in comparison to the rate of deactivation according to the mean field studies. A nonlinear dynamics model of proton dynamics is provided, which shows that the differences between stochastic and mean field simulations are due to frustrated proton state percolation.

Dataset Information

Solid Acid Resin Amberlyst 45 as a Catalyst for the Transesterification of Vegetable Oil.

Publications

Solid Acid Resin Amberlyst 45 as a Catalyst for the Transesterification of Vegetable Oil.

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