Catalytic Conversion of Levulinic Acid into 2-Methyltetrahydrofuran: A Review.

Biomass-derived furanics play a pivotal role in chemical industries, with 2-methyltetrahydrofuran (2-MTHF), a hydrogenated product of levulinic acid (LA), being particularly significant. 2-MTHF finds valuable applications in the fuel, polymer, and chemical sectors, serving as a key component in P-series biofuel and acknowledged as a renewable solvent for various chemical processes. Numerous research groups have explored catalytic systems to efficiently and selectively convert LA to 2-MTHF, using diverse metal-supported catalysts in different solvents under batch or continuous process conditions. This comprehensive review delves into the impact of metal-supported catalysts, encompassing co-metals and co-catalysts, on the synthesis of 2-MTHF from LA. The article also elucidates the influence of different reaction parameters, such as temperature, type and quantity of hydrogen source, and time. Furthermore, the review provides insights into reaction mechanisms for all documented catalytic systems.

Locally available agroresidues as potential sorbents: modelling, column studies and scale-up.

Sawdust, cotton stalk and groundnut shell were used for removal of methylene blue from aqueous solution using batch sorption. Effect of initial dye concentration, temperature, and particle size of sorbents on methylene blue removal was investigated. Sorption capacity increases with rise in initial dye concentration and temperature. Impact of particle size on sorption of methylene blue was investigated and indicated that removal of dye increases with decrease in particle size of sorbents. Maximum sorption for sawdust, cotton stalks and groundnut shell were 9.22 mg g-1, 8.37 mg g-1 and 8.20 mg g-1 respectively; at 60 °C and 100 ppm initial dye concentration. Sorption isotherms were analyzed using fundamental Freundlich isotherm. Subsequently, sips isotherm model was employed for better fitting. Kinetic study shows that, biosorption process is pseudo-second-order in nature. During the course of this study, adsorption dynamics revealed that film diffusion was key step for biosorption. In addition, thermodynamics of sorption was studied; and it was found that Gibbs free energy (∆G°) decreases with increase in temperature. Sawdust was found to be best among all the sorbents. Therefore, column studies and breakthrough curve modelling were performed using sawdust. Furthermore, it was estimated that a scaled-up column using sawdust can treat 6672 L of wastewater in 24 h with 80% efficiency.

Pilot scale oxidative fast pyrolysis of sawdust in a fluidized bed reactor: A biorefinery approach.

Oxidative fast pyrolysis of sawdust was performed in a pilot scale fluidized bed system (3 kg/h) under stabilized experimental conditions (0.20 equivalence ratio and 550 °C). Experiments were performed in non-catalytic and catalytic (ZSM-5) mode. During non-catalytic fast pyrolysis, bio-oil (∼38 wt%), bio-char (∼12 wt%) and pyro-gas (∼50 wt%) were obtained; in contrast, for catalytic fast pyrolysis bio-oil, bio-char and pyro-gas yields were ∼44 wt%, ∼4 wt% and ∼52 wt% respectively. The obtained bio-oil was characterized through CHNSO, NMR (1H and 13C NMR), FT-IR and GC-MS techniques. GC-MS analysis of the bio-oil shows it is a mixture of ∼21 chemical compounds. Furthermore, NMR (1H and 13C NMR) and FT-IR results indicates presence of hydrocarbon, alcohol, phenol and aldehyde in the bio-oil. The TGA of bio-char shows that it is stable up to 950 °C. The activation energies (Ea) of sawdust and bio-char are found to be 112.3 kJ/mol and 46.92 kJ/mol respectively. FT-IR analysis of bio-char clearly revealed removal of functionalized organic compounds during devolatilization of sawdust. In addition, GC analysis of pyro-gas suggests that it is a mixture of N2 (35.55 vol%), CO (34.49 vol%), CO2 (16.80 vol%), H2 (4.54 vol%), O2 (4.25 vol%), and CH4 (4.41 vol%).

A spent coffee grounds based biorefinery for the production of biofuels, biopolymers, antioxidants and biocomposites.

Spent coffee grounds are composed of lipid, carbohydrates, carbonaceous, and nitrogen containing compounds among others. Using n-hexane and n-hexane/isopropanol mixture highest oil yield was achived during soxhlet extraction of oil from spent coffee grounds. Alternatively, supercritical carbon dioxide can be employed as a green solvent for the extraction of oil. Using advanced chemical and biotechnological methods, spent coffee grounds are converted to various biofuels such as, biodiesel, renewable diesel, bioethanol, bioethers, bio-oil, biochar, and biogas. The in-situ transesterification of spent coffee grounds was carried out in a large scale (4 kg), which led to 80-83% biodiesel yield. In addition, a large number of value added and diversified products viz. polyhydroxyalkanoates, biosorbent, activated carbon, polyol, polyurethane foam, carotenoid, phenolic antioxidants, and green composite are obtained from spent coffee grounds. The principles of circular economy are applied to develop a sustanaible biorefinery based on valorisation of spent coffee grounds.

Conversion of lipid from food waste to biodiesel.

Depletion of fossil fuels and environmental problems are encouraging research on alternative fuels of renewable sources. Biodiesel is a promising alternative fuel to be used as a substitute to the petroleum based diesel fuels. However, the cost of biodiesel production is high and is attributed mainly to the feedstock used which leads to the investigation of low cost feedstocks that are economically feasible. In this paper, we report on the utilization of lipid obtained from food waste as a low-cost feedstock for biodiesel production. Lipid from food waste was transesterified with methanol using base and lipase as catalysts. The maximum biodiesel yield was 100% for the base (KOH) catalyzed transesterification at 1:10M ratio of lipid to methanol in 2h at 60°C. Novozyme-435 yielded a 90% FAME conversion at 40°C and 1:5 lipid to methanol molar ratio in 24h. Lipid obtained from fungal hydrolysis of food waste is found to be a suitable feedstock for biodiesel production.

Techno-economic evaluation of biodiesel production from waste cooking oil--a case study of Hong Kong.

Fossil fuel shortage is a major challenge worldwide. Therefore, research is currently underway to investigate potential renewable energy sources. Biodiesel is one of the major renewable energy sources that can be obtained from oils and fats by transesterification. However, biodiesel obtained from vegetable oils as feedstock is expensive. Thus, an alternative and inexpensive feedstock such as waste cooking oil (WCO) can be used as feedstock for biodiesel production. In this project, techno-economic analyses were performed on the biodiesel production in Hong Kong using WCO as a feedstock. Three different catalysts such as acid, base, and lipase were evaluated for the biodiesel production from WCO. These economic analyses were then compared to determine the most cost-effective method for the biodiesel production. The internal rate of return (IRR) sensitivity analyses on the WCO price and biodiesel price variation are performed. Acid was found to be the most cost-effective catalyst for the biodiesel production; whereas, lipase was the most expensive catalyst for biodiesel production. In the IRR sensitivity analyses, the acid catalyst can also acquire acceptable IRR despite the variation of the WCO and biodiesel prices.

Ionic liquid catalysed synthesis of ß-hydroxy ketones.

Different acidic ionic liquids (ILs; namely, 1-methylimidazolium tetrafluoroborate, 1-methylimidazolium trifluoroacetate, N-methyl-2-pyrrolidone hydrogen sulfate, N,N,N-trioctyl-n-butanesulfonic acid ammonium hydrogen sulfate, 1-methyl-3-(3-sulfobutyl)imidazolium hydrogen sulfate) and basic ILs (namely, 1,1,3,3-tetramethylguanidinium lactate and choline hydroxide) were tested as catalysts for the aldol reaction. The choline hydroxide catalysed reaction gave high yield (94.3%) and selectivity of the 4-hydroxy-4-phenylbutan-2-one after a short reaction time (15 min) at 0 °C. This article demonstrates the potential of choline hydroxide, which is a derivative of choline and a naturally occurring water-soluble essential nutrient, as a highly active and selective green catalyst.

Nanoparticle catalysed oxidation of sulfides to sulfones by in situ generated H2O2 in supercritical carbon dioxide/water biphasic medium.

In a one-pot reaction, hydrogen peroxide generated from H(2) and O(2) on a Pd catalyst was utilised as oxidant for the TiO(2) catalyzed conversion of a sulfide to a sulfone. This transformation, where two different nanoparticle catalysts were employed in a supercritical carbon dioxide/water biphasic system, demonstrates the potential of compartmentalising catalytic processes in consecutive reactions.

Biocatalytic synthesis of ascorbyl esters and their biotechnological applications.

Ascorbyl fatty acid esters act both as antioxidants and surfactants. These esters are obtained by acylation of vitamin C using different acyl donors in presence of chemical catalysts or lipases. Lipases have been used for this reaction as they show high regioselectivity and can be used under mild reaction conditions. Insolubility of hydrophilic ascorbic acid in non-polar solvents is the major obstacle during ascorbic acid esters synthesis. Different strategies have been invoked to address this problem viz. use of polar organic solvents, ionic liquids, and solid-phase condensation. Furthermore, to improve the yield of ascorbyl fatty acid esters, reactions were performed by (1) controlling water content in the reaction medium, (2) using vacuum to remove formed volatile side product, and (3) employing activated acyl donors (methyl, ethyl or vinyl esters of fatty acids). This mini-review offers a brief overview on lipase-catalyzed syntheses of vitamin C esters and their biotechnological applications. Also, wherever possible, technical viability, scope, and limitations of different methods are discussed.

Technical aspects of biocatalysis in non-CO2-based supercritical fluids.

The number of biotransformation processes is increasing rapidly. Part of this success is based on the inherent properties of enzymes as chemo-, regio-, and enantioselective catalysts. Supercritical fluids (scF) are superior solvents inheriting adjustable and partly unique physical properties. These can be advantageously combined with biotransformations, as solvent power responds to pressure and temperature changes according to the reaction requirements. Among the scF, supercritical carbon dioxide has undoubtedly gained the highest attention. However, other scF are also recognized to enlarge the possibilities. Among these CH(4), C(2)H(6), C(2)H(4), C(3)H(8), CHF(3), and SF(6) are used as scF for biocatalysis. This review focuses on the use of non-CO(2) based scF for biotransformations. Wherever possible, special emphasis is given on the industrial viability of different biocatalytic processes.

Preparation of biodiesel from crude oil of Pongamia pinnata.

Biodiesel was prepared from the non-edible oil of Pongamia pinnata by transesterification of the crude oil with methanol in the presence of KOH as catalyst. A maximum conversion of 92% (oil to ester) was achieved using a 1:10 molar ratio of oil to methanol at 60 degrees C. Tetrahydrofuran (THF), when used as a co-solvent increased the conversion to 95%. Solid acid catalysts viz. Hbeta-Zeolite, Montmorillonite K-10 and ZnO were also used for this transesterification. Important fuel properties of methyl esters of Pongamia oil (Biodiesel) compare well (Viscosity = 4.8 Cst @ 40 degrees C and Flash point = 150 degrees C) with ASTM and German biodiesel standards.