There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals and polymers

In pursuit of more sustainable and competitive biorefineries, the effective valorisation of lignin is key. An alluring opportunity is the exploitation of lignin as a resource for chemicals. Three technological biorefinery aspects will determine the realisation of a successful lignin-to-chemicals valorisation chain, namely (i) lignocellulose fractionation, (ii) lignin depolymerisation, and (iii) upgrading towards targeted chemicals. This review provides a summary and perspective of the extensive research that has been devoted to each of these three interconnected biorefinery aspects, ranging from industrially well-established techniques to the latest cutting edge innovations. To navigate the reader through the overwhelming collection of literature on each topic, distinct strategies/topics were delineated and summarised in comprehensive overview figures. Upon closer inspection, conceptual principles arise that rationalise the success of certain methodologies, and more importantly, can guide future research to further expand the portfolio of promising technologies. When targeting chemicals, a key objective during the fractionation and depolymerisation stage is to minimise lignin condensation (i.e. formation of resistive carbon–carbon linkages). During fractionation, this can be achieved by either (i) preserving the (native) lignin structure or (ii) by tolerating depolymerisation of the lignin polymer but preventing condensation through chemical quenching or physical removal of reactive intermediates. The latter strategy is also commonly applied in the lignin depolymerisation stage, while an alternative approach is to augment the relative rate of depolymerisation vs. condensation by enhancing the reactivity of the lignin structure towards depolymerisation. Finally, because depolymerised lignins often consist of a complex mixture of various compounds, upgrading of the raw product mixture through convergent transformations embodies a promising approach to decrease the complexity. This particular upgrading approach is termed funneling, and includes both chemocatalytic and biological strategies.

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Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading

Conversion of Biomass into Chemicals over Metal Catalysts

Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references).

http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Prednaska%207/Doplnkove%20studijne%20materialy/Hydroxymethylfurfural/Catalytic%20conversion%20of%20lignocellulosic%20biomass%20to%20fine%20chemicals%20and%20fuels.pdf

Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels

Biomass represents an abundant and relatively low cost carbon resource that can be utilized to produce platform chemicals such as levulinic acid. Current processing technology limits the cost-effective production of levulinic acid in commercial quantities from biomass. The key to improving the yield and efficiency of levulinic acid production from biomass lies in the ability to optimize and isolate the intermediate products at each step of the reaction pathway and reduce re-polymerization and side reactions. New technologies (including the use of microwave irradiation and ionic liquids) and the development of highly selective catalysts would provide the necessary step change for the optimization of key reactions. A processing environment that allows the use of biphasic systems and/or continuous extraction of products would increase reaction rates, yields and product quality. This review outlines the chemistry of levulinic acid synthesis and discusses current and potential technologies for producing levulinic acid from lignocellulosics. © 2011 Society of Chemical Industry and John Wiley & Sons, Ltd

The conversion of lignocellulosics to levulinic acid

Organosolv pretreatment of plant biomass for enhanced enzymatic saccharification

Methanesulfonic acid-catalyzed conversion of glucose and xylose mixtures to levulinic acid and furfural

Commercial furfural, an important platform chemical, is produced from acid hydrolysis of lignocellulosic biomass. The manufacturing processes are inherently inefficient, and so it is necessary to value add to substantial amounts of residue obtained. The structural features of bagasse furfural residue and the lignins extracted from it by three NaOH treatments have been studied in order to understand the transformations that occurred by these treatments. 2D-NMR and Py-GC/MS of the furfural residue revealed that it contains mostly lignin and depolymerized cellulose moieties and the complete absence of xylans as a result of their hydrolysis during the furfural production process. In addition, the analyses revealed that the furfural residue contains 44% of H-type lignin units, in comparison to 11% for bagasse, and most of the lignin interunit linkages present in bagasse have disappeared. The pyrograms show that the furfural residue produced unusually high phenol content, which was attributed to the high levels...

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Structural Characteristics of Bagasse Furfural Residue and Its Lignin Component. An NMR, Py-GC/MS, and FTIR Study

5-hydroxymethylfurfural (HMF) is a suitable platform chemical for the production of useful chemicals and fuels. This study examined the hydrolysis of mixtures of sucrose, glucose and fructose (synthetic sugar cane molasses) and industrial molasses using sulfonated carbon-based heterogeneous catalysts derived from sugar cane bagasse (B-SO3H) and sugar cane molasses (M-SO3H). Microwave heating at 150 °C for 4 h produced 39 mol % HMF yield with B-SO3H on the synthetic sugar solution. The addition of a molasses pretreatment step, as well as, increasing the microwave power was necessary to achieve similar HMF yields with the industrial molasses sample. The hydrolysis of molasses pretreated with formic acid or HCl resulted in a slightly higher HMF yield than the hydrolysis of molasses pretreated with H2SO4. The buffering capacity of the formic acid pretreated molasses was lowered through dilution with water; and subsequently HMF yield was increased to 64.3 mol % (170 °C, 3 h).

Darryn W. Rackemann

Papers

The conversion of lignocellulosics to levulinic acid

Organosolv pretreatment of plant biomass for enhanced enzymatic saccharification

Methanesulfonic acid-catalyzed conversion of glucose and xylose mixtures to levulinic acid and furfural

Structural Characteristics of Bagasse Furfural Residue and Its Lignin Component. An NMR, Py-GC/MS, and FTIR Study

Conversion of Sugar Cane Molasses to 5-Hydroxymethylfurfural Using Molasses and Bagasse-Derived Catalysts