Efficient Synthesis of Biodiesel Catalyzed by Chitosan-Based Catalysts

Catalysts play an important role in the preparation of biodiesel. It is of great significance to study catalysts with high efficiency, low cost, and easy preparation. Compared with the homogeneous catalyst system, the heterogeneous catalyst is easy to separate and has a better catalytic effect. In heterogeneous catalysts, supports and preparation methods have important effects on the dispersion of active centers and the overall performance of catalysts. However, the supports of existing solid catalysts have defects in porosity, structural uniformity, stability, and specific surface area, and the preparation methods cannot stabilize covalent bonds or ionic bonds to bind catalytic sites. Considering the activity, preparation method, and cost of the catalyst, biomass-based catalyst is the best choice, but the specific surface area of the biomass-based catalyst is relatively low, the distribution of active centers is uneven, and it is easy to lose. Therefore, the hybrid carrier of biomass-based catalyst and other materials can not only improve the specific surface area but also make the distribution of active centers uniform and the catalytic activity better. Based on this, we summarized the application of chitosan hybrid material catalysts in biodiesel. The preparation, advantages and disadvantages, reaction conditions, and so on of chitosan-based catalysts were mainly concerned. At the same time, exploring the effects of different types of chitosan-based catalysts on the preparation of biodiesel and exploring the process technology with high efficiency and low consumption is the focus of this paper.

Sintesis dan Karakterisasi Abu Kulit Alpukat sebagai Katalis Proses Transesterifikasi Minyak Goreng Bekas menjadi Biodiesel

Biodiesel is synthesized through a transesterification reaction with the help of a catalyst and generally uses a homogeneous catalyst. Heterogeneous catalysts can be synthesized from waste biomass such as avocado peel through a calcination. The purpose of this study was to examine the effect of variations in calcination temperature (550, 650, and 750oC) on the performance of the catalyst for biodiesel production and to analyze the effect of differences in the amount of catalyst (4, 6, 8, and 10% by weight of oil) used in the transesterification process on biodiesel yield. The catalysts were characterized by XRD, SEM-EDX, and FTIR. The results of the characterization of the catalyst showed that the dominant active phase of the catalyst was potassium (K). The highest biodiesel yield was obtained when using avocado peel ash as a catalyst which was calcined at a temperature of 650oC and using 6% catalyst by weight of oil. In the transesterification reaction the composition of the biodiesel product was analyzed using GC-MS and resulted that the palmitic acid was the most abundant composition in biodiesel. The biodiesel products produced were characterized for its density, viscosity, and acid number and have met the standard of SNI 7182:2015.

Synthesis and Chemical Functionalization of Pseudo-Homogeneous Catalysts for Biodiesel Production—Oligocat

With the increase in global demand for biodiesel, first generation feedstock has drawn the attention of governmental institutions due to the correlation with large land farming areas. The second and third feedstock generations are greener feedstock sources, nevertheless, they require different catalytic conditions if compared with first generation feedstock. In this work, we present the synthesis and characterization of oligoesters matrices and their functionalization to act as a pseudo-homogeneous acid catalyst for biodiesel production, named Oligocat. The main advantage of Oligocat is given due to its reactional medium interaction. Initially, oligocat is a solid catalyst soluble in the alcoholic phase, acting as a homogeneous catalyst, providing better mass transfer of the catalytic groups to the reaction medium, and as the course of the reaction happens, Oligocat migrates to the glycerol phase, also providing the advantage of easy separation of the biodiesel. Oligocat was synthesized through polymerization of aromatic hydroxy acids, followed by a chemical functionalization applying the sulfonation technique. Characterization of the catalysts was carried out by infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). The synthesized oligomers presented 5357 g·mol−1 (Mw) and 3909 g·mol−1 (Mn), with a moderate thermal resistance of approximately 175 °C. By sulfonation reaction, it was possible to obtain a high content of sulphonic groups of nearly 70 mol%, which provided the catalytic activity to the oligomeric matrix. With the mentioned physical–chemical properties, Oligocat is chemically designed to convert second generation feedstock to biodiesel efficiently. Preliminary investigation using Oligocat for biodiesel production resulted in conversion rates higher than 96.5 wt.%.

Plug-and-Play Heterogeneous Catalysis Enabled by Metal–Organic Cage-Crosslinked Polymers

The immobilization of homogeneous catalysts onto solid supports to improve recyclability while maintaining catalytic efficiency is often a trial-and-error process limited by poor control of the local catalyst environment and a lack of modular strategies to append catalysts to support materials. Here, we introduce a “plug-and-play” heterogenous catalysis platform that overcomes these challenges. Our approach leverages the well-defined interiors of self-assembled Pd12L24 metal–organic cages/polyhedra (MOCs): through a simple combination of catalyst-ligands, polymeric ligands, and spacer ligands, we demonstrate facile self-assembly of a diverse range of polymer gels featuring endohedrally-catalyst-functionalized junctions. Through decoupling catalyst incorporation and environment from the physical properties of the support (polymer matrix), this simple strategy is shown to enhance the recyclability of various catalyst systems (e.g., TEMPO-catalyzed oxidation and Au(I)-catalyzed cyclization) and enable catalysis in environments where homogeneous catalyst analogs are not viable.

Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity

Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well-established as homogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large-pore COF as catalytic support in diene ring-closing metathesis reactions, leading to increased macrocylization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF-catalyst (MMC:O = 1.30) of up to 44% compared to the homogeneous catalyst (MMC:O = 0.90) was observed along with a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement.

Synthesis of Ce/MgO Catalysts for Direct Oxidation of Hibiscus cannabinus Stalks to Vanillin

One possible method of producing vanillin from biomass is through controlled oxidation of lignin. Direct oxidation of kenaf stalks was chosen without having to separate the cellulose and hemicellulose components from the lignocellulosic biomass. This makes the process greener, as well as saving time. In this paper, Ce/MgO catalysts were developed for oxidation of kenaf stalks and kenaf lignin under microwave irradiation. The catalysts were characterized for their physicochemical properties using XRD and N2 adsorption–desorption isotherms. The synthesized MgO showed the presence of diffraction peaks assigned to cubic MgO while the 30Ce/MgO catalysts showed the presence of cubic fluorite of CeO2. N2 adsorption–desorption isotherms showed that all catalysts possess Type III isotherm according to IUPAC classification, indicating a nonporous structure. All catalysts were tested for direct oxidation of kenaf stalks under 300 W of microwave irradiation using H2O2 as the oxidizing agent at pH 11.5 and temperatures between 160 and 180 °C for 10–30 min with 5–15% catalyst loading. The highest vanillin yields of 3.70% and 2.90% for extracted lignin and direct biomass oxidation were achieved using 30Ce/MgO-48. In comparison, 7.80% and 4.45% were obtained using 2N of NaOH homogeneous catalyst for extracted lignin and direct biomass, respectively, at 170 °C for 20 min. The reusability test shows that 30Ce/MgO can be used up to three cycles without significant loss in catalytic activity. Other compounds detected were 4-vinylguaiacol, syringol and syringaldehyde.

The Kinetics Investigation of CO2 Absorption into TEA and DEEA Amine Solutions Containing Carbonic Anhydrase

Tertiary amines have been used as alternative absorbents for traditional primary and secondary amines in the process of carbon capture. However, the carbon dioxide (CO2) absorption rates in these kinds of amine are relatively slow, which implies greater investment and construction costs and limits the large-scale application of carbon capture. Carbonic anhydrase (CA) is considered to be an ideal homogeneous catalyst for accelerating the rate of CO2 into aqueous amine solution. In this work, CO2 absorption combining CA with two single aqueous tertiary amines, namely triethanolamine (TEA) and 2-(diethylamino)ethanol (DEEA), was studied by use of the stopped-flow apparatus over temperature ranging from 293 to 313 K. The concentrations of selected aqueous amine solution and CA used in the experiment were ranging among 0.1–0.5 kmol/m3 and 0–50 g/m3 , respectively. Compared to the solution without the addition of CA, the pseudo first-order reaction rate in the presence of CA (k0,withCA) is significantly increased. The values of k0,withCA have been calculated by a new kinetics model. The results of experimental and calculated k0,amine and k0,withCA in CO2-amine-H2O solutions were also investigated,respectively.