Integrated Bio- and Chemocatalytic Processing for Biorenewable Chemicals and Fuels

Alam, Md. Imteyaz; Gupta, Shelaka; Ahmạd, Ejaz; Haider, M. Ali

doi:10.1016/b978-0-444-59567-6.00006-6

Cited by 13 publications

(5 citation statements)

References 63 publications

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“…Kraus and co-workers have recently demonstrated the potential for converting triacetic acid (TAL) into 2-pyridones, to be used as pharmaceutical building blocks . TAL is analogous in structure to 6PP. − Biological synthesis of 6PP from solid state fermentation of waste biomass is reported to yield up to 7 g/L . Further experiments, utilizing genetically engineered microorganisms, are expected to increase the yield of 6PP in the fermentation reaction.…”

Section: Discussionmentioning

confidence: 99%

Alternate Biobased Route To Produce δ-Decalactone: Elucidating the Role of Solvent and Hydrogen Evolution in Catalytic Transfer Hydrogenation

Alam

Khan

Haider

2018

ACS Sustainable Chem. Eng.

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A widely used food and flavor compound, δ-decalactone (DDL), was produced from catalytic transfer hydrogenation of 6-amyl-α-pyrone (6PP), which is a biomass-based platform chemical derived through a fermentation process. The liquid phase reaction may serve as a platform to develop an integrated bio- and chemo-catalytic process for the green synthesis of DDL from lignocellulosic biomass. The catalytic transformation of 6PP to DDL was performed under mild thermal and pressure conditions over a Pd/C catalyst using formic acid as the in situ hydrogen source. The reaction in the presence of formic acid underwent complete conversion (∼99% at 433 K in 10 min) of 6PP via progressive hydrogenation of the unsaturation present in the 2-pyrone ring, leading to 79% maximum yield of DDL. On reducing the temperature from 433 to 383 K, DDL yield was observed to reduce from 79% to 2%. An ab initio microkinetic model (MKM) was constructed to understand the decomposition of formic acid with temperature variations. The MKM provided a theoretical insight into the hydrogenation reaction. The reduction in DDL yield and 6PP conversion at the lower temperatures was observed to be in direct correlation to the reduction in HCOOH decomposition rates.

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Section: Discussionmentioning

confidence: 99%

Alternate Biobased Route To Produce δ-Decalactone: Elucidating the Role of Solvent and Hydrogen Evolution in Catalytic Transfer Hydrogenation

Alam

Khan

Haider

2018

ACS Sustainable Chem. Eng.

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“…Aqueous phase pretreatment of biomass at mild temperatures (<200 °C) produces oxygenated sugar monomers of the respective cellulose and hemicellulose part . Both C 5 and C 6 sugar monomers are further upgraded via a chemical catalytic or a biocatalytic transformation to produce platform chemicals such as furfural, 5-(hydroxymethyl)furfuryl (5-HMF), levulinic acid, γ-valerolactone (GVL), 2-pyrones, etc. − The United States Department of Energy and many other reports listed biomass–derived platform chemicals which can be used to prepare an array of value added products via targeted reactions. − In general, catalytic transformation of the platform molecules involves a deoxygenation step to produce the target fuel or chemical. This step is primarily carried out by performing a combination of hydrodeoxygenation (HDO), Diels–Alder (DA), decarbonylation, dehydration, ring-opening and decarboxylation reactions. − In contrast to the carbohydrate part of the biomass, lignin requires a higher temperature (>400 °C) to yield constituent phenolic monomers such as guaiacol, catechol, etc .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Approaches toward Rational Design of a Heterogeneous Catalyst for Ring-Opening and Deoxygenation of Biomass-Derived Cyclic Compounds

Gupta

Alam

Khan

et al. 2019

ACS Sustainable Chem. Eng.

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Technologies for the processing of lignocellulosic biomass into fuels and chemicals are generally focused on selective chemical transformation of the three different types of constituents: cellulose, hemicellulose and lignin. In this regard, heterogeneous catalytic reactions are employed to defunctionalize and upgrade the platform molecules obtained selectively from these constituents. Herein, a selection of studies are discussed which are adapted to deoxygenate and valorize the biomass-derived platform molecules with a specific focus on understanding the reaction mechanisms and rational design of a heterogeneous catalyst. The selection of the deoxygenation process constituted a combination of two or three reactions. For example, ring-opening reactions of the cyclic compounds are studied with decarboxylation, dehydration, hydrogenation and/or Diels–Alder reaction carried out on metal, acid and/or oxide catalysts. The platform molecules studied here include an array of saturated lactones, 2-pyrones, cyclic ethers, furans and phenolic compounds. In the study of lactones, mechanistic insights are provided to understand the selectivity trend over the Brønsted and Lewis acid catalysts for ring-opening and decarboxylation reactions leading to the formation of α-olefins. For 2-pyrones, the integrated bio- and chemo-catalytic process is studied in which a 2-pyrone molecule obtained from fermentation media may undergo Diels–Alder, hydrogenation combined with ring-opening, decarboxylation and dehydration reactions to yield the target product. Ring-opening studies on cyclic ethers, including furanic compounds, are focused on mechanistic observations in the C–O hydrogenolysis reaction, leading to the design of bimetallic alloys to produce terminal diols and carboxylic acids. In extension to this, rational thoughts on the design of bimetallic catalysts are elucidated in the hydrodeoxygenation of the phenolic compounds.

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“…Ongoing endeavors to develop a biomass-based technology for producing fuels and chemicals are directed toward identifying a platform molecule, which is biologically or chemically derived from biomass and can be converted into a variety of fuels and chemicals via catalytic processing. − Several molecules such as lactones, levulinic acid, lactic acid, furans, etc. have been proposed as platform molecules in the list of U. S. Department of Energy’s “Top 10” biobased products from biorefinery carbohydrates. , In this continuing search, Shanks and co-workers have identified 2-pyrones as a potential platform, derived from biomass, to produce high value chemicals. ,, Recently, our group has also demonstrated the potential of 6-amyl-α-pyrone (6PP), as a biorenewable platform, produced directly from the solid state fermentation of biomass .…”

Section: Introductionmentioning

confidence: 99%

A Car–Parrinello Molecular Dynamics Simulation Study of the Retro Diels–Alder Reaction for Partially Saturated 2-Pyrones in Water

et al. 2018

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2-Pyrones have been identified as potential platform molecules derived from biomass to produce high-value chemicals. Theoretical studies utilizing density functional theory (DFT) simulations have shown the partially saturated form of these molecules undergoing a retro Diels−Alder (rDA) reaction in both vapor and solvent conditions. Developing an understanding of the effect of solvent media is crucial to improve the processing of these biomass-derived compounds. In this context, DFT simulations had shown limited access due to either implicit solvent or static explicit solvent environment applied in the model, which did not account for the contribution from the dynamics. Herein, Car−Parrinello molecular dynamics (CPMD) simulations, in conjunction with metadynamics, were performed to understand the effect of dynamics of the solvent on the rDA reaction of partially saturated 2-pyrones. For this, compounds containing both electron-donating and -withdrawing groups as substituent were studied. It was observed that, in the vapor phase, the results from CPMD simulations were in agreement with our previous DFT results. However, in water, a relative lowering in calculated activation barriers (by ∼10 kJ/mol) was observed, due to the dynamic behavior of solvent, differentially interacting with the reactant and the activated complex, along the minimum energy path. For hydroxyl substituted 2-pyrones, computed activation free energy of 63 ± 7 kJ/mol was in agreement with the apparent activation energy measured experimentally (42 ± 18 kJ/mol). CPMD-metadynamics simulations were further applied to study the reaction energetics of complex 2-pyrone molecule undergoing a similar rDA reaction.

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Integrated Bio- and Chemocatalytic Processing for Biorenewable Chemicals and Fuels

Cited by 13 publications

References 63 publications

Alternate Biobased Route To Produce δ-Decalactone: Elucidating the Role of Solvent and Hydrogen Evolution in Catalytic Transfer Hydrogenation

Alternate Biobased Route To Produce δ-Decalactone: Elucidating the Role of Solvent and Hydrogen Evolution in Catalytic Transfer Hydrogenation

Mechanistic Approaches toward Rational Design of a Heterogeneous Catalyst for Ring-Opening and Deoxygenation of Biomass-Derived Cyclic Compounds

A Car–Parrinello Molecular Dynamics Simulation Study of the Retro Diels–Alder Reaction for Partially Saturated 2-Pyrones in Water

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