Processed Lignin as a Byproduct of the Generation of 5‐(Chloromethyl)furfural from Biomass: A Promising New Mesoporous Material

Budarin, Vitaliy L.; Clark, James H.; Henschen, Jonatan; Farmer, Thomas J.; Macquarrie, Duncan J.; Mascal, Mark; Nagaraja, G. K.; Petchey, Tabitha H. M.

doi:10.1002/cssc.201501319

Cited by 13 publications

(6 citation statements)

References 52 publications

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“… 87 Such materials showed promising performances as non-noble metal electrocatalysts towards the oxygen reduction reaction. Aromatic sulfonation of lignin with sulfuric acid was also reported by Budarin et al 88 The as-synthesized sulfonated lignin particles were tested as heterogeneous acid catalysts in the esterification of levulinic acid. Hydroxyalkylation with formaldehyde has been also widely employed, in particular for the grafting of polyethylenimine through the Mannich reaction.…”

Section: From Raw To Functionalized Ligninsupporting

confidence: 58%

Expanding the biomass derived chemical space

2017

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Section: From Raw To Functionalized Ligninsupporting

confidence: 58%

Expanding the biomass derived chemical space

2017

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“…One interesting option suggested by Budarin et al, is to functionalize the by-product lignin which may be directly used as a heterogeneous acid catalysts in the alcoholysis reaction. 175 Another area which needs attention is the study of catalyst deactivation due to the presence of impurities and byproducts formed during the reaction.…”

Section: Discussionmentioning

confidence: 99%

Catalytic and mechanistic insights into the production of ethyl levulinate from biorenewable feedstocks

et al. 2016

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The importance of ethyl levulinate (EL) as a fuel additive and a potential biomassderived platform molecule is noteworthy. EL is obtained from the esterification of levulinic acid (LA) in presence of ethanol. Besides LA, the acid-catalyzed ethanolysis reaction to produce EL is carried out on a variety of biomass-derived substrates which include; furfuryl alcohol (FAL), chloromethyl furfural, monosaccharides, polysaccharides and lignocellulosic biomass. The acid catalysts employed for such conversions covers a wide range of structure and properties. The nature of acid catalysts and the key intermediates formed during the reaction dictates the overall yield of the desired product. For example, in the ethanolysis reaction of FAL to produce EL, diethyl ether (DEE) and ethoxymethylfuran (EMF) produced as side products are suggested to influence the selectivity of EL. Similarly, in the ethanolysis of glucose, formation of ethyl-Dglucopyranoside (EDGP) resulted into a slow conversion to produce EL. The review, therefore; is focused on highlighting the importance of catalyst structure, acidity, reaction mechanism and the role of key intermediates in the production of EL from biorenewable resources.EL could either be synthesized directly from biomass or via the transformation of LA, or FAL 20 or chloromethyl furfural (CMF) 23 . All of the suggested reaction routes essentially contain an ethanolysis step in the presence of an acid catalyst. In general, an understanding of the mechanistic routes of product formation, dictates the development of a suitable process for achieving higher yield 24,25 . This could be further strengthened by the design of a suitable homogeneous acid, solid acid or ionic liquid based acid catalysts. On catalytic processing, EL could be converted into an array of higher value chemicals. This review comprehensively covers all the suggested ways of EL production and applications detailing key mechanistic insights, catalytic properties and reaction conditions. Importance of EL as a Fuel AdditiveAlkyl levulinates have shown considerable promises for blending in gasoline and diesel engines, owing to their reduced sulfur content, high lubricity, improved flow properties and flash point stability 20 . The candidate LA esters for this application are methyl, ethyl 26 and butyl levulinates, 23 measuring anti-knocking index of value 106.5, 107.5 and 102.5 respectively 27 . Out of three levulinates, methyl levulinate (ML) is miscible with water and is difficult to separate. With gasoline, ML is lesser miscible and under cold flow conditions is not suitable to blend.Compared to butyl levulinate (BL), EL shows better solubility with diesel range fuels containing higher aromatics 14 . Moreover, NOx emissions were lowered by about 4% on EL blend in diesel as compared to the BL blend. Higher NOx emissions could be attributed to the dilution of lube oil and deposits in combustion chamber, which was observed to be a major problem with BL blended fuels. Furthermore, when propanol or higher alcohols are used for the...

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“…21 An intriguing discovery was that it possessed a significant degree of porosity (63 m 2 g −1 ), straight out of the reactor. 22 Most remarkably, a large fraction of this involved mesopores (pore width 2−50 nm). Pyrolysis of CMF lignin at temperatures above 400 °C dramatically increased the porosity, mainly through the generation of micropores (pore width <2 nm), while the mesopores were retained.…”

Section: Acs Sustainable Chemistry and Engineeringmentioning

confidence: 99%

“…CMF-process lignin most closely resembles Willstaetter lignin in its highly condensed character and low solubility . An intriguing discovery was that it possessed a significant degree of porosity (63 m 2 g –1 ), straight out of the reactor . Most remarkably, a large fraction of this involved mesopores (pore width 2–50 nm).…”

Section: Introductionmentioning

confidence: 99%

5-(Chloromethyl)furfural (CMF): A Platform for Transforming Cellulose into Commercial Products

Mascal

2019

ACS Sustainable Chem. Eng.

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5-(Chloromethyl)furfural (CMF) is a carbohydrate-derived platform molecule that is gaining traction as a more practical alternative to 5-(hydroxymethyl)furfural (HMF). This perspective introduces the chemocatalytic approach to biorefining as the driving force behind the development of multifunctional chemical platforms. The main advantage of CMF over HMF is that it can be produced in high yield under mild conditions directly from raw biomass. Its stability and hydrophobicity markedly facilitate isolation. CMF is also a precursor to levulinic acid (LA), another versatile biobased intermediate. The logistics of CMF production are discussed, including reactor materials, HCl handling and management, byproducts, and the fate of collateral biomass components (hemicellulose, lipids, proteins, lignin). Examples of commercial markets that can be unlocked by synthetic manipulation of CMF are broken out into two derivative manifolds, furanic and levulinic, which are distributed over three product family trees: renewable monomers, fuels, and specialty chemicals. Selected examples of CMF- and LA-based routes to these products are presented. Finally, a model for the integration of the CMF process into biorefinery practice is put forward.

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Processed Lignin as a Byproduct of the Generation of 5‐(Chloromethyl)furfural from Biomass: A Promising New Mesoporous Material

Cited by 13 publications

References 52 publications

Expanding the biomass derived chemical space

Expanding the biomass derived chemical space

Catalytic and mechanistic insights into the production of ethyl levulinate from biorenewable feedstocks

5-(Chloromethyl)furfural (CMF): A Platform for Transforming Cellulose into Commercial Products

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