Denilson Da Silva Perez

Atomic Energy and Alternative Energies Commission | CEA · Centre d'Etudes de Grenoble

Here we report the mechanocatalytic depolymerization of hemicelluloses to low molecular weight oligosaccharides. We found that the catalyst performances were severely impacted by the water content and the residual amount of alkaline-earth/alkaline metals present in hemicellulosic samples. Under optimized conditions, water soluble oligosaccharides w...

Several lignin samples of varying botanical nature (softwood, hardwood, or annual plants) and extraction procedures (Kraft, Organosolv, or soda) were fully characterized by complementary techniques and engaged in “catalyst-free” depolymerization in air under basic conditions. Treatment of the complex reaction mixture was optimized to ensure reprodu...

Biobased hard carbon is gaining attention as anode for Na-ion batteries. However, biomass composition influence on hard carbon properties and performance is rarely addressed. Here a systematic study was led on 25 biomass precursors. Woody and agricultural samples with high lignin contents (>25 weight-moisture-free, wmf%) exhibited promising yields...

The production of volatile species in torrefaction of cellulose, hemicellulose and lignin extracted from woody and agricultural biomass was quantified as a function of temperature. The novel coupling of TGA to GC/MS through a heated storage loop system allowed sampling volatile species released at 11 different temperatures in a single torrefaction...

This study investigates the impact of biomass moisture content, press-channel length, energy input, and die temperature on pellet quality in pilot-scale flat-die pellet production. In addition, observed correlations between pellet quality and the chemical composition of the pelletized biomass assortments are presented. Ten different feedstock assor...

Driftwood in river catchments might pose a hazard for the safety of infrastructures, such as dams and river dwellers, and thus is often removed. Génissiat dam in France presents a case study where annually approximately 1300 tons of driftwood are removed to prevent driftwood sinking and to protect the dam infrastructure. Collected river driftwood i...

Producing hard carbon from lignocellulosic biomass has been the focus of recent studies as a promising source of anode material for Na-ion batteries. Woody biomass is a potential source, but it is already well valorised. Consequently, river driftwood can be an excellent alternative, especially since it is a disturbing waste for dam regulators. It c...

The relation between lignin-related structure and antifungal activities was assessed against the white-rot fungus Trametes versicolor and two brown-rot fungi, Coniophora puteana and Rhodonia placenta. Various aromatic compounds were used to study the effect of lignin-related products. Guaiacyl and p-hydroxyphenyl units have hold greater antifungal...

The co-firing of solid biofuels in coal plants is an attractive and fast-track means of cutting emissions but its potential is linked to biomass densification. For torrefied materials this topic is under-represented in literature. This pilot-scale (121–203 kg h−1) pelleting study generated detailed knowledge on the densification of torrefied biomas...

Biomass composition on cellulose, hemicelluloses and lignin determinates its behavior in torrefaction (200–350 °C, default-oxygen atmosphere). Up to now, commercial microcrystalline cellulose was typically used to represent cellulose behavior in biomass torrefaction models based on macromolecular components. The objective of this work is to evaluat...

Supported gold and platinum particles on titanium oxide catalysts were evaluated in the oxidative depolymerization of lignins toward high added value aromatics under mild conditions (T: 150 °C, Pair: 20 bar, CNaOH: 10 g/L, 1 h). Kraft and ethanol Organosolv lignins were engaged in the study. Gold catalyst showed a strong tendency to further oxidize...

The poor solubility of most photosensitizers (PS) hampers their practical use as clinical agents. Conjugation of PS with water‐soluble nanoparticles has been often used to bypass this hurdle. We describe in this study the extraction of glucuronoacetylxylan from chestnut sawdust, the hemisynthesis of pheophorbide‐a (Pha) and its covalent attachment...

A series of sugar-derived triols and biobased diacids were combined to prepare fully biobased branched polyesters with different structural features by melt polycondensation. By applying the BiMolecular Non-Linear Polymerization methodology (BMNLP), the molar ratio of diacid/triols was varied to access branched polyesters bearing either hydroxyl or...

This study was performed to investigate if the process settings that give high pellet durability can be modelled from the biomass' macromolecular composition. Process and chemical analysis data was obtained from a previous pilot-scale study of six biomass assortments that by Principal Component Analysis (PCA) was confirmed as representative for the...

A new torrefaction model was proposed for predicting solid mass loss in torrefaction as a function of biomass main macromolecular composition and type, as well as on the operating conditions. To do this, solid degradation kinetics were modelled following a 2-successive reaction scheme for each macro-compound and the additive modelling approach thro...

The solvolysis of technical lignins was evaluated using water/ethanol solvent mixture with the aim of producing monomeric aromatic compounds in a continuous flow bench reactor. Four lignins issued from various biomasses (softwood, wheat straw) and extracted using different pulping processes (kraft, soda, organosolv) were engaged in the study. Befor...

The behavior of biomass in torrefaction is determined by that of its macromolecular components, as well as by the biomass type. However, up to now, commercial compounds were typically used for modelling biomass torrefaction. This work proposes to assess the behavior of cellulose, hemicelluloses and lignin in torrefaction through extracted fractions...

The influence of biomass macromolecular composition on its behaviour in torrefaction was statistically assessed through Principal Component Analysis (PCA), both in terms of solid conversion kinetics and volatile species released, in function of the operating conditions. The experimental data obtained in the torrefaction of 14 woody and agricultural...

The recovery and upgrade of hemicelluloses, a family of heteropolysaccharides in wood, is a key step to making lignocellulosic biomass conversion a cost-effective sustainable process in biorefinery. The comparative selective catalytic C-O bond hydrogenolysis of C5-C6 polyols, sugars, and their mixtures for the production of valuable C6 and C5 deoxy...

SSCI-VIDE+CDFA+NPR:MBE:CPI

Oxidation of aliphatic α,ω-diols is a potentially interesting route to the production of valuable α,ω-diacids or w-hydroxy acids for various polymer synthesis. 1,4-Butanediol (BDO), 1,5-pentanediol (PDO) and 1,6-hexanediol (HDO) are particularly attractive since they may be obtained from lignocellulosic biomass. The aqueous aerobic oxidation of the...

Several types of shrubs and oak inducing high wildland fire risk in the South of Europe were evaluated for their potential valorization through torrefaction. Biomasses were firstly characterized in terms of macromolecular and elemental composition. Lab-scale TGA-GC/MS torrefaction experiments allowed the in-depth study of the solid mass transformat...

Fractionated pyrolysis coupled to gas chromatography and mass spectrometry experiments (Py-GC/MS)were carried out on eight woody and agricultural biomasses, including beech, poplar, pine forest residues, Scot Pine bark, reed canary grass, corn cob, grape seed cake and wheat straw. The selected temperature and duration for each fractionated pyrolysi...

SSCI-VIDE+CDFA+CPI:NPR:MBE

Fractionated pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC/MS) appears as an interesting analytical tool for elucidating lignocellulosic biomass structure, as it allows the progressive release of chemical fragments representative of biomass macromolecular composition. In this paper the effect of fractionated pyrolysis time (f...

This work aims at designing functional biomaterials through selective chemical modification of xylan from beechwood. Acidic hydrolysis of xylan leaded to well-defined oligomers with an average of six xylose units per chain and with an aldehyde group at the reductive end. Reductive amination was performed on this aldehyde end-group to introduce an a...

Continuous global growth in the pellet production industry and renewable energy policy targets have driven interest in under-utilised lignocellulosic biomass. In this comprehensive study, pelleting trials were systematically carried out using a pilot-scale ring-die pellet press with eight different biomass feedstock; logging residues , pine bark, w...

Strong global growth in the pellet production industry and renewable energy policy targets have driven interest in under-utilised feedstock from forestry and agriculture. A comprehensive systematic pelleting study was carried out using a pilot-scale ring-die pellet press and eight different biomass. Investigated feedstock included forest residues,...

This poster presents the work carried out on the valorisation through torrefaction of 6 underexploided biomasses from the South of Europe usually involved in forest fires in the warm season. This work also evaluates possible impact that the application of the mobile valorization units for biomass developped in Mobile Flip project can have, especial...

Nanofibrillated cellulose (NFC) is a sustainable and renewable nanomaterial, with diverse potential applications in the paper and medical industries. As NFC consists of long fibres of high aspect ratio, we examined here whether TEMPO-(2,2,6,6-tetramethyl-piperidin-1-oxyl) oxidised NFC (length 300-1000 nm, thickness 10-25 nm), administrated by a sin...

The objective of this work is to compare mass loss and chemical evolution of the solid phase, versus time, during dynamic torrefaction of different types of biomass. For this purpose, two experiments, ThermoGravimetric Analysis and solid-state 13C Cross-Polarization/Magic Angle Spinning Nuclear Magnetic Resonance, were run on four representative bi...

This work aims at studying the sodium periodate oxidation of 4-O-methylglucuronoxylans (MGX) in different experimental conditions for a control of the oxidation degree. A series of sodium periodate oxidation reactions were conducted at three NaIO4/xylose molar ratios: 0.05, 0.20 and 1.00. The effects of xylan molar mass, xylan concentration and rea...

The aim of this paper is to study the alkali volatilization of various biomasses during steam gasification both through thermodynamic calculations and gasification experiments in a fluidized bed. Thermodynamic calculations with a database of simple compounds predicted two different alkali volatilization behaviors under the typical temperature range...

A method is described which allows prediction of alkaline pulp yield. It is based on an equation which relates the pulp yield to the cellulose content and cellulose degree of polymerization of the alkaline pulp. From the slope and intercept of this linear equation, the lignin-free pulp yield, YT′, of a pulp sample can be calculated when the lignin-...

An extensive characterization was carried out on various biomass samples representative of the diversity in France, including forestry samples (softwood and hardwood woodchips, eucalyptus and poplar short rotation coppices), very short rotation coppices (VSRC) samples and agricultural samples (wheat straw, triticale, fescue, miscanthus and switchgr...

International @ CDFA+CCB:PFO:LDJ

The purpose of this study was to design new biomaterials based on functionalized xylan derivatives. In one approach, 4-O-methylglucuronoxylan (MGX) of beechwood was oxidized by sodium periodate (NaIO4). A ratio of 0.2 NaIO4/xylose leads to a degree of oxidation of 0.15 with 75% yield. Then, the oxidized MGX aldehyde was submitted to reductive amina...

The purpose of this study was to target functionalized xylan derivatives for the design of functional materials. On the one hand, periodate oxidation was conducted on xylan from beechwood. A rate of 0.2 NaIO4/xylose leads to 5-7 oxidized units per chain. On the other hand, controlled sulfuric acidic hydrolysis of xylan from beechwood was performed...

National @ BIOVERT+CCB:PFO:LDJ

The enzymatic hydrolysis of cellulose is still considered as a main limiting step of the biological production of biofuels from ligno-cellulosic biomass. Glycoside hydrolases from Trichoderma reesei are currently used to produce fermentable glucose units from degradation of cellulose packed in a complex assembly of cellulose microfibrils. The prese...

Thin nanocomposite films of thermoplastic starch, chitosan and cellulose nanofibers (bacterial cellulose or nanofibrillated cellulose) were prepared for the first time by solvent casting of water based suspensions of the three polysaccharides. The role of the different bioploymers on the final properties (thermal stability, transparency, mechanical...

Cationizations of galactomannan- and xylan-type hemicelluloses were performed in a solid state, with 2,3-epoxypropyltrimethylammonium chloride (ETA) as the cationic reagent under alkaline conditions. By this method, the reaction efficiency was significantly increased for all hemicellulose types, up to 90% in the case of xylan. The consumption of re...

At elevated temperature, several properties of water are strongly altered compared to what our daily experience tells us: the dielectric constant of water, for example, is reduced, so that water can more easily solubilize organic molecules. In addition, the self-dissociation constant of water is increased (by three orders of magnitude at 250 degree...

The enzymatic hydrolysis of cellulose is still considered a main limiting step in the biological production of biofuel from lig-nocellulosic biomass. This step involves the action of at least three types of cellulose-degrading enzymes—endoglucanases, cellobiohydrolases, and b-glucosidases—acting in a synergis-tic way. This enzymatic cocktail, usual...

Novel bionanocomposite films with improved thermal and mechanical properties, were prepared by casting water-based suspensions of pullulan and nanofibrillated cellulose. The effect of the addition of glycerol, as a plasticizer, on the properties of the materials was also evaluated. The ensuing materials were characterized in terms of morphology, th...

The esterification of xylan type hemicelluloses, isolated from birchwood, was carried out firstly in homogeneous conditions using N,N-dimethylformamide (DMF) and lithium chloride (LiCl) in the presence of 4-dimethylaminipyridine (DMAP). The degree of substitution (DS) of xylan acetates ranged between 0.9 and 2.0 as a function of experimental condit...

Four different wood species (spruce, maritime pine, birch and eucalyptus) have been pre-extracted in different aqueous extraction liquors (acidic, near-neutral and alkaline) in order to isolated hemicelluloses prior cooking. Depending on the extraction conditions, hemicelluloses having completely different chemical composition in terms of the main...

Introduction Tree breeding is giving an increasing attention to wood properties in order to better fit the requirements of the saw, board, pulp and paper industries. In particular, it has been reported that lignin and cellulose content display moderate to high heritabilities making them prime candidates for genetic improvement of wood chemistry. M...

Biomass quality is an essential parameter for the production of biofuels both by thermal ways (gasification, pyrolysis, torrefaction, etc) or biochemical ways (enzymatic hydrolysis and yeast saccharification). Storage is one of the most important parameters to be taken in account in the logistics chains of biomass supply for biofuel conversion site...

Second-generation liquid fuels are now at the development stage that precedes their industrial implementation. They offer significant market opportunities for French lignocellulosic resources both from forests and crops. Those resources are limited and it is important to avoid competing against food crops or destabilising the sectors that already o...

Important efforts have been undertaken in the last years concerning the characterisation of biomass quality for bioenergy and/or biofuel conversion. Analytical methods for the fast evaluation of the quality of a multi-ressource biomass are then needed. Near infrared spectroscopy (NIRS) appears as one of the most promising technique for such purpose...

The goal of this work was to prepare cellulosic nanoparticles using different processing routes, viz. a combination of mechanical shearing, acid and enzymatic hydrolysis. It was shown that the enzymatic hydrolysis pretreatment of bleached sisal pulp helps the preparation of well individualized rod-like nanocrystals. The morphology of cellulose fibe...

In a previous work (Siqueira et al. 2010b) the preparation of cellulosic nanoparticles from sisal fibers using different processing routes, viz. a combination of mechanical shearing, acid and enzymatic hydrolysis was reported. It was shown that the pre-enzymatic hydrolysis treatment of bleached sisal pulp helps the preparation of well individualize...

A characterization study has been performed of the French regional resources that may be used in Biomass-to-Liquid plants based on gasification in entrained-flow reactor. It is based on about 90 representative samples of wood chips from forestry, Short Rotation Coppice (SRC) and Short Rotation Forestry (SRF) and of agricultural biomass, including s...