Depolymerization

About: Depolymerization is a research topic. Over the lifetime, 4473 publications have been published within this topic receiving 109397 citations. The topic is also known as: depolymerisation.

A review on pyrolysis of biomass constituents: Mechanisms and composition of the products obtained from the conversion of cellulose, hemicelluloses and lignin

Abstract: The conversion of biomass by thermochemical means is very promising for the substitution of fossil materials in many energy applications. Given the complexity of biomass the main challenge in its use is to obtain products with high yield and purity. For a better understanding of biomass thermochemical conversion, many authors have studied in TG analyzer or at bed scale the individual pyrolysis of its main constituents (i.e. cellulose, hemicelluloses and lignin). Based on these studies, this original work synthesizes the main steps of conversion and the composition of the products obtained from each constituent. Pyrolysis conversion can be described as the superposition of three main pathways (char formation, depolymerization and fragmentation) and secondary reactions. Lignin, which is composed of many benzene rings, gives the highest char yield and its depolymerization leads to various phenols. The depolymerization of the polysaccharides is a source of anhydro-saccharides and furan compounds. The fragmentation of the different constituents and the secondary reactions produce CO, CO2 and small chain compounds. For temperature higher than 500 °C, the residues obtained from the different constituents present a similar structure, which evolves towards a more condensed polyaromatic form by releasing CH4, CO and H2. As the aromatic rings and their substituent composition have a critical influence on the reactivity of pyrolysis products, a particular attention has been given to their formation. Some mechanisms are proposed to explain the formation of the main products. From the results of this study it is possible to predict the reactivity and energy content of the pyrolysis products and evaluate their potential use as biofuels in renewable applications.

Lignin Depolymerization and Conversion: A Review of Thermochemical Methods

Abstract: The structure of lignin suggests that it can be a valuable source of chemicals, particularly phenolics. However, lignin depolymerization with selective bond cleavage is the major challenge for converting it into value-added chemicals. Pyrolysis (thermolysis), gasification, hydrogenolysis, chemical oxidation, and hydrolysis under supercritical conditions are the major thermochemical methods studied with regard to lignin depolymerization. Pyrolytic oil and syngases are the primary products obtained from pyrolysis and gasification. A significant amount of char is also produced during pyrolysis. Thermal treatment in a hydrogen environment seems very promising for converting lignin to liquid fuel and chemicals like phenols, while oxidation can produce phenolic aldehydes. Reaction severity, solvents, and catalysts are the factors of prime importance that control yield and composition of the product.

Formic-acid-induced depolymerization of oxidized lignin to aromatics

Abstract: Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization

Abstract: Practical, high-yield lignin depolymerization methods could greatly increase biorefinery productivity and profitability. However, development of these methods is limited by the presence of interunit carbon-carbon bonds within native lignin, and further by formation of such linkages during lignin extraction. We report that adding formaldehyde during biomass pretreatment produces a soluble lignin fraction that can be converted to guaiacyl and syringyl monomers at near theoretical yields during subsequent hydrogenolysis (47 mole % of Klason lignin for beech and 78 mole % for a high-syringyl transgenic poplar). These yields were three to seven times those obtained without formaldehyde, which prevented lignin condensation by forming 1,3-dioxane structures with lignin side-chain hydroxyl groups. By depolymerizing cellulose, hemicelluloses, and lignin separately, monomer yields were between 76 and 90 mole % for these three major biomass fractions.

Formation of anhydrosugars in the chemical depolymerization of heparin.

Abstract: In the reactions used to break heparin down to mono- and oligosaccharides, androsugars are formed at two stages. The first of these is the well-known cleavage of heparin with nitrous acid to convert the N-sulfated D-glucosamines to anhydro-D-mannose residues; this reaction has been studied in detail. It is demonstrated here that only low pH (less than 2.5) reaction conditions favor the deamination of N-sulfated D-glucosamine residues; the reaction proceeds very slowly at pH 3.5 or above. On the other hand, N-unsubstituted amino sugars are deaminated at a maximum rate at pH 4 with markedly reduced rates at pH2 or pH6. At room temperature solutions of nitrous acid lose one-fourth to one-third of their capacity to deaminate amino sugars in 1 h at all pHs. A low pH nitrous acid reagent which will convert heparin quantitatively to its deamination products in 10 min at room temperature is described, and a comparison of the effectiveness of this reagent with other commonly used nitrous acid reagents is presented. It is also shown that conditions used for acid hydrolysis of heparin convert approximately one-fourth of the L-iduronosyluronic acid 2-sulfate residues to a 2,5-anhydrouronic acid. This product is an artifact of the reaction conditions, and its formation represents one of several pathways followed in the acid-catalyzed cleavage of the glycosidic bond of the sulfated L-idosyluronic acid residues.