Ethanol Coupling Reactions over MgO-Al2O3 Mixed Oxide-Based Catalysts for Producing Biofuel Additives.

Catalytic conversion of ethanol to 1-butanol was studied over MgO-Al2O3 mixed oxide-based catalysts. Relationships between acid-base and catalytic properties and the effect of active metal on the hydrogen transfer reaction steps were investigated. The acid-base properties were studied by temperature-programmed desorption of CO2 and NH3 and by the FT-IR spectroscopic examination of adsorbed pyridine. Dispersion of the metal promoter (Pd, Pt, Ru, Ni) was determined by CO pulse chemisorption. The ethanol coupling reaction was studied using a flow-through microreactor system, He or H2 carrier gas, WHSV = 1 gEtOH·gcat.-1·h-1, at 21 bar, and 200-350 °C. Formation and transformation of surface species under catalytic conditions were studied by DRIFT spectroscopy. The highest butanol selectivity and yield was observed when the MgO-Al2O3 catalyst contained a relatively high amount of strong-base and medium-strong Lewis acid sites. The presence of metal improved the activity both in He and H2; however, the butanol selectivity significantly decreased at temperatures ≥ 300 °C due to acceleration of undesired side reactions. DRIFT spectroscopic results showed that the active metal promoted H-transfer from H2 over the narrow temperature range of 200-250 °C, where the equilibrium allowed significant concentrations of both dehydrogenated and hydrogenated products.

Two-stage conversion of high free fatty acid Jatropha curcas oil to biodiesel using Brønsted acidic ionic liquid and KOH as catalysts.

Biodiesel was produced from high free fatty acid (FFA) Jatropha curcas oil (JCO) by two-stage process in which esterification was performed by Brønsted acidic ionic liquid 1-(1-butylsulfonic)-3-methylimidazolium chloride ([BSMIM]Cl) followed by KOH catalyzed transesterification. Maximum FFA conversion of 93.9% was achieved and it reduced from 8.15 wt% to 0.49 wt% under the optimum reaction conditions of methanol oil molar ratio 12 : 1 and 10 wt% of ionic liquid catalyst at 70 °C in 6 h. The ionic liquid catalyst was reusable up to four times of consecutive runs under the optimum reaction conditions. At the second stage, the esterified JCO was transesterified by using 1.3 wt% KOH and methanol oil molar ratio of 6 : 1 in 20 min at 64 °C. The yield of the final biodiesel was found to be 98.6% as analyzed by NMR spectroscopy. Chemical composition of the final biodiesel was also determined by GC-MS analysis.

Biodiesel Production from Chlorella homosphaera by Two-Step Catalytic Conversion Using Waste Radish Leaves as a Source for Heterogeneous Catalyst.

The economic viability of algal biodiesel can be improved by enhancing the microalgal lipid accumulation and using agricultural waste as a cheap and sustainable source of catalysts. In the current study, the effect of various nitrogen concentrations on the growth and lipid of Chlorella homosphaera were investigated. Furthermore, two-step catalytic conversion was applied to convert the oil of C. homosphaera with high free fatty acids (FFA) to biodiesel using waste radish leaves as a source of a heterogeneous base catalyst. The result revealed that the maximum lipid productivity of 25.0 mg L-1 day-1 and lipid content of 30.83% were obtained under nitrogen-depleted and limited nitrogen conditions, respectively. The FFA was reduced from 18.79 to 0.76%, and the acid value was decreased from 37.4 to 1.52 mg KOH g-1 using a 15:1 methanol to oil molar ratio (MTOR), 1.5 wt.% H2SO4, at 60 °C for 150 min. Under the optimized conditions, i.e., MTOR of 10:1, 3 wt.% of catalyst ratio for 120 min at 60 °C, the highest oil conversion of 96.61% was obtained. The physicochemical properties of the produced biodiesel were in the range of the standard specification norms for biodiesel. Hence, the proposed two-step catalytic conversion using calcined radish leaves as a heterogeneous catalyst has thus exhibited good potential for biodiesel production using algal oil with high FFA.

Towards integrated sustainable biofuel and chemical production: An application of banana pseudostem ash in the production of biodiesel and recovery of lignin from bamboo leaves.

This study investigated an integrated approach to the biowaste transformation and valorization of byproducts. Biochar obtained from the banana pseudostem was calcined to synthesize a heterogeneous catalyst and sustainably prepare a highly alkaline solution. The ash was utilized directly as a heterogeneous catalyst in biodiesel production from waste cooking oil. At the same time, an alkaline solution prepared from the ash was used for delignification and recovery of lignin from bamboo leaves by the hydrothermal reaction. Techniques like Fourier-transform infrared spectroscopy (FTIR), Field emission scanning electron microscopy (FESEM), Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM), and Energy dispersive X-ray (EDX) were applied to characterized the catalyst. The alkaline solution was analyzed with Atomic absorption spectroscopy (AAS). The Response surface methodology (RSM) technique was considered for the optimization of different parameters in the transesterification and hydrothermal reaction. Under the optimized condition, waste cooking oil (WCO) to Fatty acid methyl ester (FAME) conversion was 97.56 ± 0.11%, and lignin recovery was 43.20 ± 0.45%. While at the best operating pyrolysis temperature, the liquid fraction yield from the banana pseudostem (500 °C) was 38.10 ± 0.31 wt%. This integrated study approach encourages the inexpensive, sustainable, and environment-friendly pathway for synthesizing catalysts and preparing a highly alkaline solution for the valorization of biowaste into biofuel and biochemicals.

Ecofriendly phytofabrication of silver nanoparticles using aqueous extract of Cuphea carthagenensis and their antioxidant potential and antibacterial activity against clinically important human pathogens.

The green synthesis of nanoparticles (NPs) is the safest, ecofriendly, cost-effective, and non-hazardous approach of nanotechnology. In the current study, we described the green synthesis of silver nanoparticles (AgNPs) using Cuphea carthagenensis aqueous leaf extract as a reducing, capping, and stabilizing agent. The study aims at the synthesis, characterization, optimization, and determination of the antibacterial activity of Cc-AgNPs against clinically important human pathogens. Coating of cotton fabrics with Cc-AgNPs and their efficacy against skin infection causing organisms was also evaluated. Furthermore, antioxidant activity, growth assay and time kill assay of Cc-AgNPs were also performed in the study. The biosynthesized Cc-AgNPs were characterized by UV-visible spectrometry, energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR). The spectroscopic and microscopic analysis demonstrated biosynthesis of face-centered cubic (fcc) crystalline spherical Cc-AgNPs with an average particle size of 10.65 ± 0.1 nm. Optimized peak synthesis of Cc-AgNPs was reported at pH7, 55 °C, 4 mM silver nitrate, and 5:45 (plant extract: silver nitrate). Cc-AgNPs exhibited potent antioxidant effect and antibacterial activity against both Gram-positive and Gram-negative bacteria. The lowest MIC (15 µg/ml) and MBC (25 µg/ml) values were reported against S. typhimurium. The Cc-AgNPs coated fabrics demonstrated potent antibacterial activity against tested strains. This application could be helpful in wound healing management. Furthermore, the hemolytic analysis demonstrated that Cc-AgNPs exhibit non-toxic nature against Red Blood Cells (RBCs) at the tested concentrations. In conclusion, the investigation demonstrated a fast, stable, and eco-friendly approach to the biosynthesis of Cc-AgNPs along with their antibacterial and antioxidant properties.

Towards sustainable biodiesel and chemical production: Multifunctional use of heterogeneous catalyst from littered Tectona grandis leaves.

Waste biomass derived heterogeneous catalyst is an excellent alternative to chemically synthesized catalysts. In this work, calcined Tectona grandis leaves were proposed as an eco-friendly, renewable and low cost heterogeneous base catalyst. The prepared catalyst was examined by FTIR, XRD, XPS, SEM, EDX, TEM, TGA, BET and Hammett indicator test. The catalyst has an appealing nature towards various chemical transformations due to its basic surface sites provided by alkali and alkaline earth metals. The efficiency of the catalyst was successfully investigated by its application in biodiesel production. The products were confirmed by 1H and 13C NMR. 100% FAME conversion was attained using a catalyst loading of 2.5 wt% under optimized reaction parameters. The catalyst was further explored for Knoevenagel condensation reaction, in which it showed its effectiveness and recyclability towards the formation of benzylidenemalononitrile derivatives of aryl aldehydes. Thus, it is a potential 'green catalyst' derived from waste biomass without any addition of chemicals that can replace the industrial base catalysts used for biodiesel production and Knoevenagel reaction and makes the protocol environmentally benign.

Enhanced catalytic activity and near room temperature gas sensing properties of SnO2 nanoclusters@mesoporous Sn(iv) organophosphonate composite.

A simple, facile and one-pot route for preparing SnO2 nanoclusters embedded on a mesoporous Sn(iv) organophosphonate (MSnP) framework is described. Reaction of SnCl4·5H2O with a flexible tris-phosphonic acid, mesityl-1,3,5-tris(methylenephosphonic acid), in the presence of a surfactant under hydrothermal conditions produced the desired nanocomposite, SnO2@MSnP. Analytical, spectroscopic and microscopic studies establish that SnO2@MSnP composite is comprised of SnO2 nanoparticles of an average size of 5 nm evenly and abundantly dispersed over the MSnP framework. The mesoporous metal organophosphonate support significantly augments the catalytic efficacy and vapor sensitivity of SnO2 nanoparticles. The catalytic efficiency of SnO2@MSnP was tested for two acid-catalyzed reactions: deoximation reaction and esterification of fatty acids. SnO2@MSnP exhibits remarkable sensitivity towards ammonia and acetone vapors at near room temperature and under open atmospheric conditions. The present method represents an important step towards preparation of mesoporous metal organophosphonate supported metal oxide nanoclusters and hence offers easy access to functional metal oxide based nanocomposites.

Removing antinutrients from rapeseed press-cake and their benevolent role in waste cooking oil-derived biodiesel: conjoining the valorization of two disparate industrial wastes.

Valorization of oilseed processing wastes is thwarted due to the presence of several antinutritional factors such as phenolics, tannins, glucosinolates, allyl isothiocyanates, and phytates; moreover, literature reporting on their simultaneous extraction and subsequent practical application is scanty. Different solvent mixtures containing acetone or methanol pure or combined with water or an acid (hydrochloric, acetic, perchloric, trichloroacetic, phosphoric) were tested for their efficiency for extraction of these antinutritive compounds from rapeseed press-cake. Acidified extraction mixtures (nonaqueous) were found to be superior to the nonacidified ones. The characteristic differences in the efficacy of these wide varieties of solvents were studied by principal component analysis, on the basis of which the mixture 0.2% perchloric acid in methanol/acetone (1:1 v/v) was deemed as "the best" for detoxification of rapeseed meal. Despite its high reductive potential, hemolytic activity of the extract from this solvent mixture clearly indicated the toxicity of the above-mentioned compounds on mammalian erythrocytes. Because of the presence of a high amount of antinutritive antioxidants, the study was further extended to examine the influence of this solvent extract on the stability of waste cooking oil-derived biodiesel. Treatment with the extract harbored significant improvement (p < 0.05) in the induction periods and pronounced reduction in microbial load of stored biodiesel investigated herein. Thus, a suitable solvent system was devised for removing the major antinutrients from rapeseed press-cake, and the solvent extract can, thereafter, be used as an effective exogenous antioxidant for biodiesel. In other words, integrated valorization of two different industrial wastes was successfully achieved.