scispace - formally typeset
Search or ask a question
Journal ArticleDOI

Hydrolysis of Cellulose by Amorphous Carbon Bearing SO3H, COOH, and OH Groups

TL;DR: The carbon catalyst can be readily separated from the saccharide solution after reaction for reuse in the reaction without loss of activity, and the catalytic performance of the carbon catalyst is attributed to the ability of the material to adsorb beta-1,4 glucan, which does not adsorb to other solid acids.
Abstract: The hydrolysis of cellulose into saccharides using a range of solid catalysts is investigated for potential application in the environmentally benign saccharification of cellulose. Crystalline pure cellulose is not hydrolyzed by conventional strong solid Bronsted acid catalysts such as niobic acid, H-mordenite, Nafion and Amberlyst-15, whereas amorphous carbon bearing SO 3H, COOH, and OH function as an efficient catalyst for the reaction. The apparent activation energy for the hydrolysis of cellulose into glucose using the carbon catalyst is estimated to be 110 kJ mol (-1), smaller than that for sulfuric acid under optimal conditions (170 kJ mol (-1)). The carbon catalyst can be readily separated from the saccharide solution after reaction for reuse in the reaction without loss of activity. The catalytic performance of the carbon catalyst is attributed to the ability of the material to adsorb beta-1,4 glucan, which does not adsorb to other solid acids.
Citations
More filters
Journal ArticleDOI
TL;DR: The various hemicelluloses structures present in lignocellulose, the range of pre-treatment and hydrolysis options including the enzymatic ones, and the role of different microbial strains on process integration aiming to reach a meaningful consolidated bioprocessing are reviewed.

1,355 citations


Cites background from "Hydrolysis of Cellulose by Amorphou..."

  • ...…(polystyrene-based cation-exchangeable resin with SO3H), sulfonated activated-carbon, and amorphous carbon bearing SO3H, COOH and OH (Chung et al., 1992; Onda et al., 2009; Suganuma et al., 2008), as well as other materials such as bentonite, kaolin and acid-treated alumina (Blair et al., 2009)....

    [...]

  • ...Lignin may mainly remains insoluble (Suganuma et al., 2008; Yamaguchi et al., 2009), or also be solubilised (Blair et al., 2009), in what is probably a function of the catalyst nature....

    [...]

Journal ArticleDOI
TL;DR: 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.
Abstract: 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).

1,123 citations

Journal ArticleDOI
TL;DR: In this article, the authors showed that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignins conversion of about 50%.
Abstract: Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization.

744 citations

Journal ArticleDOI
TL;DR: Past and present developments in hydrogenolysis reactions are highlighted, with special emphasis on the direct utilization of cellulosic feedstocks, to bridge currently available technologies and future biomass-based refinery concepts.
Abstract: In view of the diminishing oil resources and the ongoing climate change, the use of efficient and environmentally benign technologies for the utilization of renewable resources has become indispensible. Therein, hydrogenolysis reactions offer a promising possibility for future biorefinery concepts. These reactions result in the cleavage of C-C and C-O bonds by hydrogen and allow direct access to valuable platform chemicals already integrated in today's value chains. Thus, hydrogenolysis bears the potential to bridge currently available technologies and future biomass-based refinery concepts. This Review highlights past and present developments in this field, with special emphasis on the direct utilization of cellulosic feedstocks.

735 citations

References
More filters
Journal ArticleDOI
TL;DR: In this paper, a model and theoretical understanding of the Raman spectra in disordered and amorphous carbon is given, and the nature of the G and D vibration modes in graphite is analyzed in terms of the resonant excitation of \ensuremath{\pi} states and the long-range polarizability of the long range bonding.
Abstract: The model and theoretical understanding of the Raman spectra in disordered and amorphous carbon are given. The nature of the G and D vibration modes in graphite is analyzed in terms of the resonant excitation of \ensuremath{\pi} states and the long-range polarizability of \ensuremath{\pi} bonding. Visible Raman data on disordered, amorphous, and diamondlike carbon are classified in a three-stage model to show the factors that control the position, intensity, and widths of the G and D peaks. It is shown that the visible Raman spectra depend formally on the configuration of the ${\mathrm{sp}}^{2}$ sites in ${\mathrm{sp}}^{2}$-bonded clusters. In cases where the ${\mathrm{sp}}^{2}$ clustering is controlled by the ${\mathrm{sp}}^{3}$ fraction, such as in as-deposited tetrahedral amorphous carbon (ta-C) or hydrogenated amorphous carbon (a-C:H) films, the visible Raman parameters can be used to derive the ${\mathrm{sp}}^{3}$ fraction.

12,593 citations

Book
01 Jan 1963
TL;DR: In this paper, a sequence of procedures for identifying an unknown organic liquid using mass, NMR, IR, and UV spectroscopy is presented, along with specific examples of unknowns and their spectra.
Abstract: Presents a sequence of procedures for identifying an unknown organic liquid using mass, NMR, IR, and UV spectroscopy, along with specific examples of unknowns and their spectra,

11,753 citations

Journal ArticleDOI
27 Jan 2006-Science
TL;DR: The integration of agroenergy crops and biorefinery manufacturing technologies offers the potential for the development of sustainable biopower and biomaterials that will lead to a new manufacturing paradigm.
Abstract: Biomass represents an abundant carbon-neutral renewable resource for the production of bioenergy and biomaterials, and its enhanced use would address several societal needs. Advances in genetics, biotechnology, process chemistry, and engineering are leading to a new manufacturing concept for converting renewable biomass to valuable fuels and products, generally referred to as the biorefinery. The integration of agroenergy crops and biorefinery manufacturing technologies offers the potential for the development of sustainable biopower and biomaterials that will lead to a new manufacturing paradigm.

5,344 citations

Journal ArticleDOI
TL;DR: It is suggested that it is timely to revisit and reinvigorate functional modeling of cellulose hydrolysis and that this would be highly beneficial if not necessary in order to bring to bear the large volume of information available on cellulase components on the primary applications that motivate interest in the subject.
Abstract: Information pertaining to enzymatic hydrolysis of cellulose by noncomplexed cellulase enzyme systems is reviewed with a particular emphasis on development of aggregated understanding incorporating substrate features in addition to concentration and multiple cellulase components. Topics considered include properties of cellulose, adsorption, cellulose hydrolysis, and quantitative models. A classification scheme is proposed for quantitative models for enzymatic hydrolysis of cellulose based on the number of solubilizing activities and substrate state variables included. We suggest that it is timely to revisit and reinvigorate functional modeling of cellulose hydrolysis, and that this would be highly beneficial if not necessary in order to bring to bear the large volume of information available on cellulase components on the primary applications that motivate interest in the subject.

1,852 citations

Journal ArticleDOI
TL;DR: This review gives an overview of the new technologies required and the advances achieved in recent years to bring lignocellulosic ethanol towards industrial production.

1,477 citations