Catalyst For Transesterification Research Articles

Transesterification of waste cooking oil for biodiesel production using alkaline-modified graphitic carbon nitride heterogeneous catalyst

ABSTRACT Developing efficient, stable, cost-effective, and environmentally benign heterogeneous catalysts for transesterification is highly required for sustainable biodiesel production. The present study explores the biodiesel production from waste cooking oil (WCO) using graphitic carbon nitride (g-C3N4) and its alkaline-modified nanocatalyst. The catalysts were characterised by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDS), and Fourier transform infrared spectroscopy (FTIR). From the XRD analysis, crystalline sizes of g-C3N4 and alkaline g-C3N4 were found to be 26 and 29 nm, respectively. Transesterification of WCO was carried out at 60 °C for a reaction time of 2 h using 2 wt.% of g-C3N4 and alkaline g-C3N4. Transesterification reaction catalysed by alkaline-modified g-C3N4 was found with a higher yield of biodiesel (89%) than the biodiesel yield (78%) with transesterification reaction catalysed by g-C3N4. The recyclability of both catalysts was also evaluated by reusing them for up to the 5th cycle. The obtained biodiesel was analyzed by using FTIR and GC-MS. The synthesised biodiesel was found to have significant level of monounsaturated fatty acids and saturated fatty acids, which make it usefuel for use as fuel. Some physicochemical properties of the obtained biodiesel were also calculated and found appropriate as per the American Society for Testing and Materials (ASTM) standards. With high reusability and good catalytic activity, the synthesised alkaline-modified g-C3N4 can be employed as a viable option for biodiesel production from WCO.

Maximization of Micractinium sp., biomass and use of Dual-Purpose reduced graphene supported vanadium oxide nanoparticles for harvesting and subsequent biodiesel production

A sustainable media composition comprising of nanourea (NU), groundnut de-oiled cake (GDOC), and seaweed Extract (SE) was formulated using a mixture design for the cultivation of Micractinium sp. Maximum biomass yield and productivity of 5.52 ± 0.09 g/L and 0.72 ± 0.03 g/L d−1 were observed at 1.67 mM NU, 0.134 g/L GDOC and 0.250 mL L−1 SE, respectively. The highest lipid yield of 2.73 ± 0.24 g/L was also observed, respectively. The reduced graphene-supported vanadium oxide nanoparticles (RGO-VNPs) with a net surface charge of + 34.10 mV were developed, which acted as a % as well as a catalyst for transesterification. A maximum flocculation efficiency of 98 % was observed with 200 ppm of RGO-VNPs. The Fatty Acid Methyl Ester (FAME) yield of 96.81 ± 1.61 % was observed. Thus, the present study could provide a plausible solution for one-pot harvesting and synthesis of biodiesel utilizing microalgal lipids.

Transesterification Catalyst Strength as Observed by solution-based Oxygen-17 Nuclear Magnetic Resonance Spectroscopy

Transesterification Catalyst Strength as Observed by solution-based Oxygen-17 Nuclear Magnetic Resonance Spectroscopy

Valorization of Glycerol to Glycerol Carbonate and Glycidol by Different Dialkyl Carbonates Utilizing Tricalcium Aluminate Hexahydrate as Transesterification Catalyst

AbstractIn this study, we report a base‐catalyzed transesterification reaction of glycerol, a waste product of the biodiesel industry, with various dialkyl carbonates, which act both as reactants and solvents, to convert glycerol carbonate into an industrially useful molecular building block. The catalyst, being used for the first time, is also a waste product from industry, present in bauxite residues and in the Portland cement, simply known as tricalcium aluminate. Despite being well‐known and readily available, this solid is only extremely poorly researched catalyst, nevertheless, using dimethyl and diethyl carbonate, glycerol conversion rates >80% and glycerol carbonate yields >60% could be achieved in just 1 h (under air atmosphere and reflux). In a comparison of the performance with other catalysts commonly researched today, as well as with other components of red mud and cements, the results showed that tricalcium aluminate is excellent, cheap, and largely environmentally friendly material for this purpose. Reusability studies of the catalysts have also shown that they provide high conversion and product yields even after repeated use, although different material characterization techniques showed intense glycerol‐catalyst surface interaction and intermediate product formation, the deactivating side effects of which could be avoided by catalyst regeneration steps.

Comparative Studies on Methyl Ester Production from Pretreated Sludge Palm Oil Using Homogeneous and Heterogeneous Base Catalysts

A heterogeneous base catalyst transesterification process with a calcium oxide (CaO) catalyst was performed to produce high-purity methyl ester (ME) from pretreated sludge palm oil (PSPO) derived from sludge palm oil (SPO). Additionally, a comparative analysis was conducted with potassium hydroxide (KOH) as a homogeneous base catalyst to assess the distinctions between heterogeneous and homogeneous base catalysts. The response surface methodology (RSM) was utilized to determine the optimal and recommended conditions for both transesterification processes. For heterogeneous transesterification, a varying CaO catalyst loading (10–60 wt.%), methanol (25–65 wt.%), and reaction time (60–180 min) were essential parameters. Meanwhile, homogeneous transesterification involved investigating the KOH catalyst loading (1–3 wt.%), methanol (1.8–5.5 wt.%), and reaction time (20–60 min). For the heterogeneous-base-catalyzed reaction, the recommended conditions were as follows: a molar ratio of methanol to oil of 5.83:1 (41.61 wt.%), 31.3 wt.% CaO, and a reaction time of 119.0 min, which resulted in a ME purity of 96.51 wt.%. The optimal conditions for homogeneous transesterification were a molar ratio of methanol to oil of 0.49:1 (3.45 wt.%), a 40 min reaction time, and a 1.39 wt.% KOH concentration, which achieved 96.59 wt.% ME and met the standard.

Thermal activation of basic oxygen furnace slag as a heterogeneous catalyst in transesterification: Characterization and catalytic activity studies

The valorization of industrial by-products has garnered significant attention in recent years due to its potential to enhance sustainability and economic efficiency within various sectors. Basic Oxygen Furnace slag (BOF-S), a by-product generated in the steelmaking process characterized by its complex composition, presents an opportunity for waste management and resource recovery. This study investigates the potential of BOF-S as a catalyst in converting waste cooking oil to biodiesel via the transesterification reaction. To improve its efficiency, BOF-S was calcined at 850 °C (BOF-S 850), and 1000 °C (BOF-S 1000), for 5 h. The BOF-S was characterized using XRF, N2 sorption, XRD, TGA-DSC, SEM-EDS and FTIR. The characterization techniques showed that the BOF-S 850 had superior characteristics as a catalyst: rough surface, increased pore size and more active basic sites compared to the BOF-S and the BOF-S 1000 slag samples. The transesterification reaction was conducted at a methanol: oil ratio of 20:1, a catalyst loading of 20 wt %, a reaction time of 12 h, a reaction temperature of 60 °C, and a stirring speed of 750 rpm. The findings established that the BOF-S 850 was the best catalyst, with a 90.77 % biodiesel yield and was able to sustain a maximum of two transesterification cycle runs.

Influence of Solid Alkaline Photocatalysts Irradiated with UV Light on Fuel Properties of Palm Oil Biodiesel.

TiO2 nanoparticles are full of porosity that can be impregnated with a strong alkaline catalyst CH3ONa to form a TiO2/CH3ONa catalyst. TiO2 of the anatase phase, which is a semiconductor material, has been a prominent photocatalyst due to its excited photocatalyst activity, chemical and biological stability, and nontoxicity. The CH3ONa compound has been widely used as a catalyst for transesterification. Although the synthesized photocatalyst TiO2 powder with CH3ONa is anticipated to greatly enhance the transesterification efficiency, leading to improving biodiesel properties, relevant studies have not been found. After the photocatalyst was prepared, a reactant mixture of palm oil, methanol, and heterogeneous catalyst TiO2/CH3ONa was illuminated by ultraviolet (UV) light from light-emitting diode (LED) lamps. The experimental results revealed that the formation of fatty acid methyl esters was significantly increased to 98.4% with ultraviolet-light illumination for the molar ratio of methanol/palm oil equal to 6 and 3 wt % catalyst addition. The decrease of the catalyst amount to 2 wt % resulted in a slight decrease of the fatty acid methyl esters to 97.06 wt %. The lowest kinematic viscosity and acid value and the highest distillation temperature, heating value, and cetane index were observed under the above reaction conditions. The distillation temperature and cetane index were increased while the acid value was decreased under ultraviolet illumination on the reactant mixture. Consequently, the optimum preparing conditions for biodiesel production were 6 and 3 wt % for the molar ratio of methanol/palm oil and catalyst addition under UV-light irradiation.

In-situ stabilized lipase in calcium carbonate microparticles for activation in solvent-free transesterification for biodiesel production

Biodiesel serves as a crucial biofuel alternative to petroleum-based diesel fuels, achieved through enzymatic transesterification of oil substrates. This study aims to investigate stabilized lipase (LP) within calcium carbonate (CaCO3) microparticles as a catalyst for solvent-free transesterification in biodiesel synthesis. The specific hydrolysis activity of the in-situ immobilized LP was 66% of that of free LP. However, the specific transesterification activity of immobilized LP in the solvent-free phase for biodiesel production was 2.29 times higher than that of free LP. These results suggest that the interfacial activation of LP molecules is facilitated by the inorganic CaCO3 environment. The immobilized LP demonstrated higher biodiesel production levels with superior stability compared to free LP, particularly regarding methanol molar ratio and temperature. To the best of our knowledge, there are no previous reports on the in-situ immobilization of LP in a CaCO3 carrier without any crosslinker as an interfacial-activated biocatalyst for biodiesel production.

Rejuvenating liquid crystal elastomers for self-growth

To date, only one polymer can self-grow to an extended length beyond its original size at room temperature without external stimuli or energy input. This breakthrough paves the way for significant advancements in untethered autonomous soft robotics, eliminating the need for the energy input or external stimuli required by all existing soft robotics systems. However, only freshly prepared samples in an initial state can self-grow, while non-fresh ones cannot. The necessity of synthesizing from monomers for each use imposes significant limitations on practical applications. Here, we propose a strategy to rejuvenate non-fresh samples to their initial state for on-demand self-growth through the synergistic effects of solvents and dynamic covalent bonds during swelling. The solvent used for swelling physically transforms the non-fresh LCEs from the liquid crystal phase to the isotropic phase. Simultaneously, the introduction of the transesterification catalyst through swelling facilitates topological rearrangements through exchange reactions of dynamic covalent bonds. The rejuvenation process can also erase growth history, be repeated several times, and be regulated by selective swelling. This strategy provides a post-modulation method for the rejuvenation and reuse of self-growing LCEs, promising to offer high-performance materials for cutting-edge soft growing robotics.

Fe-doped TiO2 nanocrystals as highly efficient catalysts for heterogeneous catalytic transesterification of coconut oil

BackgroundThe impact of Fe doped TiO2 nanocatalyst on the heterogeneous catalytic transesterification reaction of coconut oil into biodiesel has been investigated. MethodsThe nanocatalyst was prepared by sol-gel method using titanium isopropoxide as TiO2 precursor and Fe(NO3)3 as iron (Fe) source. Several conditions of Fe-TiO2 were synthesized, each with Fe concentration of 0.5 %, 1 %, and 1.5 %, and calcined at 500 °C. The nanocatalyst's physical and chemical characteristics including phase crystallinity and morphology were examined. Significant findingsWe found that the biodiesel conversion efficiency increases with the increasing of Fe content in the Fe-TiO2 nanocatalyst and optimum at the Fe concentration of 1.5 % (w/w). The optimal Fe-TiO2 nanocatalyst could yield biodiesel output as high as 30.8 %, under at a relatively low temperature of 60 °C. Furthermore, the presence of the nanocatalyst effectively reduced the free fatty acid content in the biodiesel product by 1.43 %. Moreover, the acidity of the produced biodiesel was exceptionally low, at 0.02 %, primarily attributed to lauric acid. These exceptional performances are believed to be attributed to the enhanced surface chemistry properties of the Fe-TiO2 nanocatalyst. The Fe-TiO2 system is expected to find extensive application in the cost-effective production of biodiesel.

Compatibilizing and foaming of PC/PMMA composites with nano‐cellular structures in the presence of transesterification catalyst

AbstractCompatibility of polycarbonate (PC) and polymethyl methacrylate (PMMA) alloys was improved by using a transesterification catalyst (SnCl2·2H2O). Modified PC/PMMA alloys exhibit single Tg, and their initial island phase existing in the SEM were transformed into uniform surface. Besides, the transmittance of the modified alloys was increased from original 40% to 85%. Moreover, PC/PMMA alloys and PC foams with micro‐cellular and nano‐cellular structures were prepared by solid‐state CO2 foaming in the presence of transesterification catalyst. Distinctively, there are obvious nano‐cellular structures existing in the PC samples, but no related nanostructures were found in PMMA samples, after treated by same amount of catalyst and foaming process for pure PC and PMMA matrix. Furthermore, the effects of foaming temperature and segment structure on their foaming behavior were also studied. Additionally, a uniaxial stress experiment was conducted at a specific temperature to simulate the biaxial stress during the foaming process for discovering the mechanism of nanopore formation. Therefore, the concept of nano‐cellular structures will point out a direction for the development of high‐performance, heat insulation PC materials of the next generation.Highlights Transesterification catalysts enhanced compatibility between PC and PMMA. Nanopore structures were successfully constructed in PC foams. Segment stretching was the main reason for the formation of nanopores.

Comparison of potassium catalysts on zeolite sodium A and X in transesterification of palm oil and active species specification

Heterogeneous catalysts consisting of potassium supported on zeolites are active for transesterification, but the effect of zeolite properties is not clearly understood. This work compares catalysts containing 12 wt.% potassium on zeolite sodium A and X (12K/NaA and 12K/NaX) in terms of performance and physicochemical properties. Both catalysts were prepared by ultrasound-assisted impregnation with potassium acetate buffer. 12K/NaA is a better catalyst in transesterification of palm oil, giving a higher biodiesel yield than 12K/NaX in the first run (99.1 ± 0.3 % and 77.9 ± 2.2 %, respectively). From characterization by CO2-TPD, XRD, FTIR, XPS, and SEM-EDS, both catalysts have similar basicity but different dispersion of carbonates and interaction on the zeolites. The 12K/NaA has those species on external surfaces and more monodentate carbonate than 12K/NaX. Ion exchange occurs between potassium ions from the precursor and sodium ions from the zeolite. Moreover, 12K/NaA is more stable, providing higher biodiesel yields in the second and third catalytic cycles.

Effectiveness of empty fruit bunch ash as the catalyst for palm oil transesterification

Empty Fruit Bunch (EFB) resulted from oil palm plantations and mills can be converted into ash through open combustion. The EFB ash then treated by simple calcination and used as a heterogeneous catalyst for biodiesel production. The characteristics of EFB ash were identified based on its elemental composition, porous structure, and active site size. The effectivity of the EFB ash as a catalyst was tested in a transesterification reaction of Refined Bleached Deodorized Palm Oil (RBDPO) with excess methanol (30 %-w) in various catalyst loads (in%-wt). The lab-scale experiments were conducted in a three-neck glass reactor, which was put on the hot plate stirrer at 450 rpm. The EFB ash performed the best as a catalyst by attaining optimal conversion at 65 °C for 1 h with a 16 %-wt of catalyst load. In this condition, most of the standard quality of biodiesel were complied with total glycerol under 0.24% and ester methyl contents up to 98.9 %. The characteristics tests showed that the properties and active side of the EFB ash are excellent after calcination at 600 for 5 h. The recyclability test of EFB ash as a catalyst showed high performance in two repetition cycles, each showing an increase in the yield of biodiesel, which was 92.21 % in cycle 2 and 91.23 % in cycle 3.

Degradation of a Wholly Aromatic Main-Chain Thermotropic Liquid-Crystalline Polymer Mediated by Superbases.

Plastic circular economy needs to be established to solve environmental issues related to plastic waste. Superengineering plastics such as liquid-crystalline (LC) polymers exhibit excellent thermal and mechanical properties, resulting in poor degradability in natural environment. Herein, we report the degradation of a wholly aromatic thermotropic LC polyester, poly(4-hydroxybenzoic acid-co-6-hydroxy-2-naphthoic acid) (Vectra) mediated by superbases. Methanolysis and hydrolysis of Vectra yield its monomeric compounds, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and their methyl esters. Among several transesterification catalysts explored, 1,5,7-triazabicylco[4.4.0]dec-5-ene (TBD) is the most suitable for the methanolysis of Vectra. The complete degradation of Vectra is achieved under reflux. The degradation proceeds heterogeneously via a surface erosion mechanism, preferentially starting from less chain-packed regions. Model reactions using aryl arylates reveal that monomeric compound-superbase complexes could mediate the cleavage of the ester bonds in both homogeneous and heterogeneous systems. The ester bonds of Vectra have inherent poor reactivity and are protected by oriented robust structures of the polymer. Nevertheless, the superbases enable the degradation of Vectra via the cleavage of the ester bonds by methanol. These outcomes open the way for recycling high-performance plastics as well as demonstrate the feasibility of recovering precious aromatic compounds from plastic waste as aromatic feedstock.

Contribution of Malang quartzite-based silica in K2O/zeolite Y catalyst for methyl ester synthesis of off grade crude palm oil

Malang quartzite contains a highly silica content. The silica changes the structural composition of Zeolite Y. Currently, a heterogeneous catalyst is developed to optimize transesterification of Off Grade CPO (Crude Palm Oil). The aims of this study are: (1) synthesize K2O/Zeolite Y using silica from Malang quartzite, (2) synthesize methyl esters from Off Grade CPO using K2O/Zeolite Y catalyst, and (3) to evaluate quartzite based-silica contribution in Zeolite Y for the reaction activity via GC-MS analysis. The experimental stages were: the oil preparation, esterification of the prepared oil, preparation of K2O/zeolite Y catalyst, and the transesterification. This study applied variations of [KOH] in Zeolite Y (10, 20, and 30 % w/w) and the concentration of the transesterification catalyst (2, 3, and 4 % w/w). The K2O/Zeolite Y catalyst was successfully synthesized by impregnation method. Methyl esters of Off Grade CPO resulted the highest yield of 95.05 % with 4 wt% of 30-K2O/Zeolite Y (30 % KOH impregnation). The synthesized methyl esters have a density of 0.877 g/mL, a viscosity of 4.6 cSt, a refractive index of 1.445 and an acid number of 0.384 mg/g according to the standard (SNI 7182:2015). The main components of the methyl ester based on GC-MS results were methyl octanoate, methyl decanoate, methyl dodecanoate, methyl 9-octadecanoate, methyl octadecanoate and methyl tetracosanoate. Using quartzite-based silica, a co-activity of the reaction has occurred.

Using NaOH@Graphene oxide-Fe3O4 as a magnetic heterogeneous catalyst for ultrasonic transesterification; experimental and modelling

Burning fossil fuels causes toxic gas emissions to increase, therefore, scientists are trying to find alternative green fuels. One of the important alternative fuels is biodiesel. However, using eco-friendly primary materials is a main factor. Sustainable catalysts should have high performance, good activity, easy separation from reaction cells, and regenerability. In this study, to solve the mentioned problem NaOH@Graphene oxide-Fe3O4 as a magnetic catalyst was used for the first time to generate biodiesel from waste cooking oil. The crystal structure, functional groups, surface area and morphology of catalyst were studied by XRD, FTIR, BET, and FESEM techniques. The response surface methodology based central composite design (RSM-CCD) was used for biodiesel production via ultrasonic technique. The maximum biodiesel yield was 95.88% in the following operation: 10.52:1 molar ratio of methanol to oil, a catalyst weight of 3.76 wt%, a voltage of 49.58 kHz, and a time of 33.29 min. The physiochemical characterization of biodiesel was based to ASTM standard. The magnetic catalyst was high standstill to free fatty acid due to the five cycle’s regeneration. The kinetic study results possess good agreement with first-order kinetics as well as the activation energy and Arrhenius constant are 49.2 kJ/min and 16.47 * 1010 min−1, respectively.

Reshapable bio-based thiol-ene vitrimers for nanoimprint lithography: Advanced covalent adaptability for tunable surface properties

Taking inspiration from natural surfaces known for their ability to adaptively remodel their shape, we fabricated stimuli-responsive microstructures by using UV-induced nanoimprint lithography. For this, a fully bio-based dynamic thiol-ene photopolymer was synthetized by the radical mediated addition of a trifunctional eugenol-based thiol (SH3E) crosslinker across an allylated linseed oil (ALELO). To catalyze the bond exchange reactions between the hydroxyl and ester groups within the network, a bio-based eugenol phosphate ester was introduced as a transesterification catalyst. Pure eugenol was further added as a reactive diluent to increase the number of hydroxyl groups and thus, accelerate the thermo-activated bond exchange reactions. Once cured by UV exposure, the dynamic photopolymer is thermally stable up to 250 °C and is able to relax 63% of the original stress within 62 min at 160 °C. Subsequently, films with micropillars, having an aspect ratio of 1:2.5 were prepared by using nanoimprint lithography. The macroscopic reflow capability of the dynamic network enabled a reorientation of the imprinted structures during a thermal reshaping step. The imprints were characterized by 2D/3D optical microscopy, μCT imaging and static water contact angle measurements. Based on the orientation of the micropillars, the water contact angle was varied between 118° and 95°, giving rise to a possible application in microfluidic devices.

KF/MgO used as the catalyst for transesterification of dimethyl carbonate with isosorbide to dicarboxymethyl isosorbide

KF/MgO used as the catalyst for transesterification of dimethyl carbonate with isosorbide to dicarboxymethyl isosorbide

Facile and efficient fabrication of carbon nanotube reinforced epoxy vitrimers through dynamic crosslinking

AbstractCarbon nanotubes (CNT) is an ideal candidate for reinforced epoxy vitrimer composites, however, achieving a desirable improvement of the mechanical properties is a great challenge owing to CNT is extremely easy to aggregate. In this study, well‐dispersed CNT reinforced epoxy vitrimers, namely EVD/CNT, were prepared by combining ultrasonic dispersion and dynamic crosslinking techniques, using multiple wall carbon nanotube as reinforcement filler, sebacic acid as curing agent, diglycidyl ether of bisphenol A (DGEBA) as epoxy monomer, zinc acetylacetonate as transesterification catalyst, torque rheometer (internal mixer) as dynamic crosslinking equipment. The CNT reinforced epoxy vitrimers, namely EVS/CNT, were prepared using traditional static curing method. The structure and morphology, mechanical properties and stress relaxation behavior of EVS/CNT and EVD/CNT were comparatively investigated, and the influence of CNT content on the structure and properties of EVD/CNT prepared by dynamic crosslinking method were also studied. The results indicated that dynamic crosslinking technology can stably disperse CNT into epoxy vitrimer resin matrix under continuous shear force. However, CNT experienced severe secondary agglomeration during the static curing process. When the loading amount of CNT was 2 wt%, the tensile strength and elongation at break of EVD/CNT‐2 were 3.2 times and 2.2 times higher than those of EVS/CNT‐2, respectively. The Young's modulus and glass transition temperature (Tg) of EVD/CNT‐2 (6.43 ± 1.10 MPa, 29.6°C) were also higher than those of EVS/CNT‐2 (5.46 ± 0.31 MPa, 25.4°C). Moreover, dynamic crosslinking technology greatly shortened the reaction time of CNT reinforced epoxy vitrimers, improved production efficiency and reduced reaction energy consumption, and was expected to be used for large‐scale and industrial production.

Water‐Assisted Reprocessing and Shape Programming of Epoxy Vitrimer

Water‐Assisted Reprocessing and Shape Programming of Epoxy Vitrimer