Wege zur Verwertung von Lignin: Fortschritte in der Biotechnik, der Bioraffination und der Katalyse

Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.; Ralph, John; Kennema, Marco; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

doi:10.1002/ange.201510351

Cited by 162 publications

(22 citation statements)

References 415 publications

(566 reference statements)

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“…Generally,t he calibration still suffered from the clear structural differencesb etween standards and analytes, notwithstanding the fact that commercially available PSS standards (with or without sulfonic-acid groups)are structurally closest to lignin among the available standards.L ignin molar-mass analysisb ys mall-angle neuron scattering revealed its much denser structure than typical for linear polymers usedf or calibration. [26] Hence, the structure of lignin in solutiona ppears more compact similart oh yperbranched polymers or nanogels and polystyrene calibration represents ar elative methodo nly.…”

Section: Resultsmentioning

confidence: 99%

Fast Track to Molar‐Mass Distributions of Technical Lignins

Sulaeva

Zinovyev

Plankeele³

et al. 2017

ChemSusChem

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Technical lignins (waste products obtained from wood pulping or biorefinery processes) have so far required lengthy analysis procedures and different eluents for molar-mass analysis by gel permeation chromatography (GPC). This challenge has become more pressing recently since attempts to utilize lignins have increased, leading to skyrocketing numbers of samples to be analyzed. A new approach, which uses the eluent DMSO/LiBr (0.5 % w/v) and converts lignosulfonate salts into their acidic form before analysis, overcomes these limitations by enabling measurement of all kinds of lignins (kraft, organosolv, soda, lignosulfonates) in the same size-exclusion chromatography (SEC) system without the necessity of prior time-consuming derivatization steps. In combination with ultra-performance liquid chromatography (UPLC), analysis times are shortened to one tenth of classical lignin GPC. The new approach is presented, along with a comparison of GPC and UPLC methods and a critical discussion of the analytical parameters.

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Section: Resultsmentioning

confidence: 99%

Fast Track to Molar‐Mass Distributions of Technical Lignins

Sulaeva

Zinovyev

Plankeele³

et al. 2017

ChemSusChem

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“…We further applied the PtCo/NOMC-2 catalyst for HDO of al ignin-derived non-pyrolytic bio-oil, which had been obtained from early-stage catalytic conversion of lignin (ECCL) [16] through hydrogen transfer reaction in the presence of Raney Ni and 2-propanol. [2] Through this approach, lignin is depolymerized directly after its extraction from plant biomass in ao ne-pot process.A dvantageously,i ni ts composition, the lignin oil stream mostly comprises monocyclic phenols and, to al esser extent, alcohols and phenolic oligomers.M oreover,a sE CCL directly reduces carbonyl functionalities (associated with ketones and aldehydes), the lignin oil stream is obtained as at hermally stable stream.…”

Section: Angewandte Chemiementioning

confidence: 99%

Nitrogen‐Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics

Wang

Cao

et al. 2016

Angewandte Chemie

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Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance.H erein we report an ovel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3m) structure can be easily synthesized by simply adjusting the polymerization temperature.W ea lso demonstrate that PtCo/NOMC (metal loading:P t9 .90 wt %; Co 3.31 wt %) is ah ighly effective catalyst for HDO of phenolic compounds and "real-world" biomass-derived phenolic streams.I nt he presence of PtCo/NOMC,f ull deoxygenation of phenolic compounds and ab iomass-derived phenolic stream is achieved under conditions of lows everity.Bio-oils are mixtures of highly functionalized oxygenates obtained by pyrolytic [1] or non-pyrolytic [2] processes performed on lignocellulose.A ne ssential step in the utilization of bio-oils as af eedstock for the production of biofuels constitutes the catalytic upgrading,t hat is,t he removal of oxygen-containing groups from the bio-oils (oxygen content: 30-50 wt %). This step improves the stability of the bio-oils, and increases the energy density,sothat properties similar to those of conventional fossil, oil-based, transportation fuels are achieved. [3] Hydrodeoxygenation (HDO), ahighly attractive route for upgrading of bio-oils,i nvolves reactions of the bio-oil with hydrogen to produce hydrocarbons and water. [1] Many catalysts for HDO processes have been studied, and they include metals (e.g., Pt, Pd, Ru, Rh, Fe,N i, Co), metal sulfides (e.g.,C oMo-and NiMo-based sulfides), metal phosphides (e.g., Ni 2 Pa nd Co 2 P), metal carbides (e.g., W 2 C and Mo 2 C), or related compounds. [4] Recently,wefound that bimetallic PtCo nanoparticles (ca. 3.6 nm) in hollow carbon nanospheres show high activity for hydrogenolysis of 5hydroxymethylfurfural to 2,5-dimethylfuran with 98 % yield. [5] Such catalysts are capable of hydrodeoxygenating C=Oa nd CÀOH groups without the drawbacks associated with the use of acidic supports (i.e.t he promotion of side reactions,e.g., dehydration, cracking,and polymerization;the polymerization reaction contributes to catalyst deactivation via formation of carbonaceous deposits on the metal particles). [4a,b] Therefore,wehypothesized that the bimetallic PtCo catalysts should also be conducive to efficient upgrading of biomass-derived phenolic streams.To utilize the active PtCo components efficiently,o ne approach is to downsize the bimetallic PtCo nanoparticles and finely disperse them on supports.T he supports should allow efficient mass transfer,a nd suppress sintering and loss of the active catalyst during the HDO process.N itrogendoped ordered mesoporous carbon (NOMC) meets these requirements as ar esult of ac ombination of properties,t h...

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“…[3] In particular, owing to its unique phenylcontaining monomers, lignin is an important renewable source of aromatic compounds. [5] However,t he rigid, irregular, and highly cross-linked structure of lignin represents a significant challenge to effective degradation despite considerable efforts. [5] However,t he rigid, irregular, and highly cross-linked structure of lignin represents a significant challenge to effective degradation despite considerable efforts.…”

Section: Introductionmentioning

confidence: 99%

“…[4] The development of efficient processes for the valorization of lignin is aw ell-recognized objective. [5] However,t he rigid, irregular, and highly cross-linked structure of lignin represents a significant challenge to effective degradation despite considerable efforts. [6] Currenti ndustrial chemical catalytic and microbial reactions destroy the majority of valuablea romatic units and functional groups in lignin.…”

Section: Introductionmentioning

confidence: 99%

Conversion of Lignin Models by Photoredox Catalysis

Zhang

2018

ChemSusChem

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One prominent goal of 21st century research is to develop a sustainable carbon-neutral biorefinery. Lignin is an important component of lignocellulosic biomass; however, it is currently underutilized owing to its highly cross-linked, complex, and randomly polymerized composition, which poses a significant challenge to its depolymerization and valorization. Chemical catalytic approaches based on transition metals represent the primary research area to drive degradation reactions. Recently, alternative photocatalytic strategies that employ sustainable solar energy to initiate the transformation of lignin have started to emerge. This Concept article examines new developments of photocatalyzed reactions and provides insight into C-O and C-C bond-cleavage reactions of lignin models in both homogeneous and heterogeneous systems.

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Wege zur Verwertung von Lignin: Fortschritte in der Biotechnik, der Bioraffination und der Katalyse

Cited by 162 publications

References 415 publications

Fast Track to Molar‐Mass Distributions of Technical Lignins

Fast Track to Molar‐Mass Distributions of Technical Lignins

Nitrogen‐Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics

Conversion of Lignin Models by Photoredox Catalysis

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