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Item Synthesis of highly-branched alkanes for renewable gasoline(Elsevier B.V., 2020) Mascal, M.; Dutta, S.The gasoline market in the US is nearly twice that of diesel and jet fuel combined, and yet, nearly all research efforts to produce synthetic, biobased fuels center around these latter products. The reason for this is that a major component of gasoline is highly branched alkanes which, unlike straight chained products, are not readily derived from either fatty acid- or carbohydrate-based feedstocks. This review unpacks the motivations behind renewable gasoline synthesis and examines representative approaches to the targeted, de novo synthesis of densely-branched, high-octane isoalkanes and cycloalkanes employing chemocatalytic methods, as contrasted with the catalytic refining of biomass-derived feeds using petrochemical technologies. © 2019 Elsevier B.V.Item Recent advances in the preparation of levulinic esters from biomass-derived furanic and levulinic chemical platforms using heteropoly acid (HPA) catalysts(Elsevier B.V., 2021) Bhat, N.S.; Mal, S.S.; Dutta, S.The esters of biomass-derived levulinic acid (LA) have several potential applications, including cleaner-burning fuel additive, green solvent, fragrance ingredient, and a renewable chemical intermediate for downstream value addition. The levulinic esters (LEs) can be prepared by the acid-catalyzed alcoholysis of the biomass-derived furanic and levulinic chemical platforms such as LA, furfuryl alcohol (FAL), 5-(hydroxymethyl)furfural (HMF), and angelica lactone (AGL). The acid-catalyzed deconstruction of carbohydrates in an alcoholic medium affords the one-pot preparation of LEs. Choosing the right catalyst is of paramount importance for synthesizing LEs from both the economic and environmental perspectives. In this regard, heteropoly acids (HPAs), a class of polyoxometalates (POMs) bearing protons as the counter cation, have found widespread applications as acid catalysts in various organic transformations. HPAs are blessed with conducive properties such as controlled Brønsted and Lewis acidity, high thermal stability, robust structural features, non-toxic nature, tunable solubility, and less corrosiveness. Over the past several years, HPAs have found extensive applications as efficient and environment-friendly catalysts in biorefinery operations, including the synthesis of LEs. At this juncture, it is imperative to ascertain the achievements in this field to date and re-evaluate the challenges. This review attempts to provide up-to-date information about the preparation of LEs using HPA-based catalysts, critically analyze the literature cited, draw conclusions, and propose future prospects. © 2021 Elsevier B.V.Item Synthesis of renewable carbon biorefinery products from susceptor enhanced microwave-assisted pyrolysis of agro-residual waste: A review(Institution of Chemical Engineers, 2022) Rajasekhar Reddy, B.R.; Sridevi, V.; Kumar, T.H.; Sankar Rao, C.S.; Palla, V.C.S.; Suriapparao, D.V.; Undi, G.S.Valuable renewable carbon biorefinery products can be obtained by using agro-residual biomass as a feedstock. Bio-oil, gas, and char products can be obtained from Microwave-assisted pyrolysis (MAP) by converting agro-residual waste. In MAP, the process variables like microwave power, temperature, heating rate, raw materials, susceptors, and catalysts play an important role to alter the product spectrum. The temperature, heating rate, and pyrolysis time can be tuned to obtain the desired products during biomass decomposition. The obtained carbonaceous products can be used as intermediated feedstocks to synthesize a variety of end products. Hence, in this review, the application of MAP for the conversion of agro-residual waste is discussed. Special focus is given to the interaction of microwaves with susceptors. This manuscript provides background, current status, progress, and future scope of MAP technology for waste valorization. The objectives of the review are to address (i) The necessity of environmental protection, (ii) The role of biorefinery in the biomass conversion, (iii) The advancements in the MAP for the resource recovery, (iv) The mechanism of heat generation from microwaves, (v) The effects of process parameters, susceptors, and catalysts in MAP, (vi) The interactions of biomass and susceptors during the pyrolysis, (vii) The formation of valuable renewable carbon products and (viii) The future scope and challenges for the integration of MAP in solid waste management. © 2022 The Institution of Chemical EngineersItem Catalytic synthesis of renewable p-xylene from biomass-derived 2,5-dimethylfuran: a mini review(Springer Science and Business Media Deutschland GmbH, 2023) Dutta, S.; Bhat, N.S.In this work, the renewable synthesis of p-xylene (PX) from biomass-derived carbohydrates has been reviewed. PX is a crucial chemical feedstock and an essential starting material of polyethylene terephthalate (PET). PX can be produced selectively by the Diels-Alder reaction between ethylene and 2,5-dimethylfuran (DMF) followed by catalytic dehydration of the oxanorbornene adduct. DMF is primarily produced by the catalytic hydrogenation of 5-(hydroxymethyl)furfural (HMF), a furanic intermediate produced by the acid-catalyzed hydrolysis/dehydration of biomass-derived hexoses. With ethylene being sourced by dehydrating bioethanol, PET can be made biorenewable in its entirety. The atom economy and carbon efficiency of converting glucose into PX have been calculated. The existing literature (both theoretical and experimental) on the catalytic production of PX from DMF and ethylene are summarized, and future directions on this research have been proposed. The effect of Brønsted and Lewis acidity, porosity, and surface area of the heterogeneous catalysts on the selectivity and yield of PX have been highlighted. In addition, the techno-economic analysis of renewable PET, its future prospects based on the petroleum market, and the possibility of a circular economy of PET using chemical and enzymatic recycling strategies have been discussed. © 2020, Springer-Verlag GmbH Germany, part of Springer Nature.Item Recent advances in the production and value addition of selected hydrophobic analogs of biomass-derived 5-(hydroxymethyl)furfural(Springer Science and Business Media Deutschland GmbH, 2023) Anchan, H.N.; Dutta, S.5-(Hydroxymethyl)furfural (HMF), produced by the acid-catalyzed dehydration of biomass-derived hexoses, is a well-recognized renewable chemical intermediate in the biorefinery research for the productions of fuels, chemicals, and materials. However, the inherent hydrophilicity and poor stability of HMF continue to disfavor its production and value addition from an economic standpoint. In this regard, the superior thermal and hydrolytic stability of the hydrophobic analogs of HMF simplify their isolation and purification from the aqueous (or polar) reaction media while enhancing their shelf life. The analogs show promises in supplanting HMF from its derivative chemistry. The halogenated derivatives of HMF, such as 5-(chloromethyl)furfural (CMF) and 5-(bromomethyl)furfural (BMF), can be produced directly from biomass in good isolated yields. The non-halogenated, hydrophobic derivatives of HMF include esters such as 5-(formyloxymethyl)furfural (FMF) and 5-(acetoxymethyl)furfural (AMF), obtained by the dehydration of carbohydrates in suitable carboxylic acids. The ethers of HMF, such as 5-(ethoxymethyl)furfural (EMF), can be produced directly by the acid-catalyzed alcoholysis of biomass. In addition, partially oxidized or reduced derivatives of HMF, such as 2,5-diformylfuran (DFF) and 5-methylfurfural (5MF), have also found significant interests as hydrophobic analogs of HMF. The production and value addition of various lipophilic analogs of HMF are rather scattered in the literature, and no comprehensive review is available in this area to date. This technical review attempts to fill that gap with up-to-date information with a critical analysis of the achievements and challenges. In this review, the production and derivative chemistry of various hydrophobic analogs of HMF have been discussed. The relative advantages and challenges associated with the preparation and value addition of various hydrophobic analogs of HMF are highlighted. Graphical abstract: [Figure not available: see fulltext.]. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.Item Valorization of biomass-derived furfurals: reactivity patterns, synthetic strategies, and applications(Springer Science and Business Media Deutschland GmbH, 2023) Dutta, S.The expertise of synthetic organic chemistry accumulated over the past century has been instrumental in converting biomass to fuels, chemicals, and materials. Particular emphasis has been attributed to using eco-friendly reagents and reaction conditions by adhering to the principles of green chemistry. Catalysis remains at the heart of organic synthesis and has a ubiquitous presence in the organic chemistry literature. Not surprisingly, catalytic processes are increasingly used in the chemistry of renewables under commercially relevant and environmentally acceptable conditions. In this review, the synthesis of various biofuels and renewable chemicals from biomass-derived furfural and 5-(hydroxymethyl)furfural has been elaborated. Synthetic upgrading of furfurals has been shown in the light of chemical modifications of the reactive sites present in them. This review aims to provide a critical understanding of the influence of synthetic organic chemistry in biomass value addition via the furanic platform. This work will encourage the researchers to improve the existing synthetic pathways, develop new synthetic strategies, and broaden the scope of applications for biorenewable products. Graphical abstract: [Figure not available: see fulltext.]. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.Item Biological phenol removal using immobilized cells in a pulsed plate bioreactor: Effect of dilution rate and influent phenol concentration(2007) Shetty K, K.V.; Ramanjaneyulu, R.; Srinikethan, G.The continuous aerobic biodegradation of phenol in synthetic wastewater was carried out using Nocardia hydrocarbonoxydans immobilized over glass beads packed between the plates in a pulsed plate bioreactor at a frequency of pulsation of 0.5 s-1 and amplitude of 4.7 cm. The influence of dilution rate and influent phenol concentration on start up and steady state performance of the bioreactor was studied. The time taken to reach steady state has increased with increase in dilution rate and influent phenol concentration. It was found that, as the dilution rate is increased, the percentage degradation has decreased. Steady state percentage degradation was also reduced with increased influent phenol concentration. Almost 100% degradation of 300 and 500 ppm influent phenol could be achieved at a dilution rate of 0.4094 h-1 and more than 99% degradation could be achieved with higher dilution rates. At a higher dilution rate of 1.0235 h-1 and at concentrations of 800 and 900 ppm the percentage degradation has reduced to around 94% and 93%, respectively. The attached biomass dry weight, biofilm thickness and biofilm density at steady state were influenced by influent phenol concentration and dilution rate. © 2007 Elsevier B.V. All rights reserved.Item Studies on exhaust emissions of mahua oil operated compression ignition engine(2009) Kapilan, N.; Reddy, R.P.The world is confronted with fossil fuel depletion and environmental degradation. The energy demand and pollution problems lead to research for an alternative renewable energy sources. Vegetable oils and biodiesel present a very promising alternative fuel to diesel. In this work, an experimental work was carried out to study the feasibility of using raw mahua oil (MO) as a substitute for diesel in dual fuel engine. A single cylinder diesel engine was modified to work in dual fuel mode and liquefied petroleum gas (LPG) was used as primary fuel and mahua oil was used as pilot fuel. The results show that the performance of the dual fuel engine at the injector opening pressure of 220 bar and the advanced injection timing of 30°bTDC results in performance close to diesel base line (DBL) operation and lower smoke and oxides of nitrogen emission.Item Production of propyl gallate in nonaqueous medium using cell-associated tannase of Bacillus massiliensis: Effect of various parameters and statistical optimization(2013) Aithal, M.; Belur, P.D.Enzymatic synthesis of propyl gallate in an organic solvent was studied using cell-associated tannase (E.C. 3.1.1.20) of Bacillus massiliensis. Lyophilized biomass showing tannase activity was used as a biocatalyst. The influence of buffer pH and strength, water activity, temperature, biocatalyst loading, gallic acid concentration, and 1-propanol concentration was studied by the one-factor-at-a-time method. Subsequently, response surface methodology was applied based on a central composite design to determine the effects of three independent variables (biocatalyst loading, gallic acid concentration, and 1-propanol concentration) and their mutual interactions. A total of 20 experiments were conducted, and a statistical model was developed, which predicted the maximum propyl gallate yield of 20.28 ?g/mL in the reaction mixture comprising 40.4 mg biocatalyst, 0.4 mM gallic acid, and 6.52 % (v/v) 1-propanol in 9.5 mL benzene at 30°C. The subsequent verification experiments established the validity of the model. Under optimal conditions, 25% conversion of gallic acid to propyl gallate was achieved on a molar basis. The absence of the need for enzyme purification and subsequent immobilization steps and good conversion efficiency makes this enzyme system an interesting one. Reports on the applications of bacterial whole cell systems for synthetic reactions in organic solvents are scarce, and perhaps this is the first report on bacterial cell-associated tannase-mediated esterification in a nonaqueous medium. © 2013 International Union of Biochemistry and Molecular Biology, Inc.Item Multistrain probiotic production by co-culture fermentation in a lab-scale bioreactor(Wiley-VCH Verlag info@wiley-vch.de, 2016) Jangra, M.; Belur, P.D.; Oriabinska, L.B.; Dugan, O.M.Most commercial probiotic products intended for pharmaceutical applications consist of combinations of probiotic strains and are available in various forms. The development of co-culture fermentation conditions to produce probiotics with the correct proportion of viable microorganisms would reduce multiple operations and the associated costs. The aim of this study was to develop a fermentation medium and process to achieve biomass comprising the desired proportion of two probiotic strains in co-culture. Initially, a quantification medium was developed, and the method was optimized to allow the quantification of each strain's biomass in a mixture. The specific growth rates of Lactobacillus delbrueckii spp. bulgaricus and Lactobacillus plantarum were determined in media with different carbon sources. The inoculum volume was optimized to achieve equal proportion of biomass in co-culture fermentation in test tubes. Next, fermentation was carried out in a 3-L bioreactor. A biomass concentration of 2.06 g/L, with L. delbrueckii spp. bulgaricus and L. plantarum in the ratio of 47%:53% (by weight), was achieved with concomitant production of 12.69 g/L of lactic acid in 14 h. The results show that with careful manipulation of process conditions, it is possible to achieve the desired proportion of individual strains in the final biomass produced by co-culture fermentation. This process may serve as a model to produce multistrain probiotic drugs at industrial scale. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.