Jalel Labidi

Ultrasound-assisted fractionation of the lignocellulosic material

In the present work the effectiveness of different lignocellulosic biomass fractionation processes based on ultrasounds technology was evaluated. Organosolv (acetic acid 60% v/v), alkaline (sodium hydroxide 7.5% w/w) and autohydrolysis treatments were applied at low temperature and the fractionation effectiveness was measured at different sonication conditions of the raw material. The obtained solid fractions were characterized using TAPPI standard methods, and the liquid fractions main components were quantified with the purpose of studying the effect that the treatment conditions had on the obtained by-products quality. Therefore, obtained lignin samples were characterized by ATR-IR spectroscopy and their thermal behaviour by TGA technique. The results showed that ultrasounds application improved the yield and selectivity of the studied processes and that the obtained lignin did not suffer significant modifications in its physicochemical properties.

Effect of alkaline and autohydrolysis processes on the purity of obtained hemicelluloses from corn stalks

A study of the potential of autohydrolysis and alkaline extraction processes from corn stalks was performed for high purity hemicellulose extraction. The influence of process parameters on the purity of obtained hemicelluloses was analyzed. An experimental design was developed for the autohydrolysis treatments to determine the optimal conditions to solubilize the hemicelluloses with lowest content in contaminants. On the other hand, alkaline extraction, including raw material pretreatment (dewaxing and delignification step) was carried out analyzing the effectiveness of this processes for maximum pure hemicellulose recovery. The maximum yield (54% of the raw material hemicelluloses) and the best physicochemical properties (highest hemicellulose content free of lignin) were obtained with these pretreatments in alkaline extraction. Moreover, the effect of lignin removal by sulfuric acid from the autohydrolysis liquors before hemicellulose precipitation was studied. This purification step has allowed to obtain lignin-free autohydrolysis hemicellulose but with the presence of sulfur as predominant contaminant.

Processing of α-chitin nanofibers by dynamic high pressure homogenization: characterization and antifungal activity against A. niger.

Chitin nano-objects become more interesting and attractive material than native chitin because of their usable form, low density, high surface area and promising mechanical properties. This work suggests a straightforward and environmentally friendly method for processing chitin nanofibers using dynamic high pressure homogenization. This technique proved to be a remarkably simple way to get α-chitin into α-chitin nanofibers from yellow lobster wastes with a uniform width (bellow 100 nm) and high aspect ratio; and may contributes to a major breakthrough in chitin applications. Moreover, the resulting α-chitin nanofibers were characterized and compared with native α-chitin in terms of chemical and crystal structure, thermal degradation and antifungal activity. The biological assays highlighted that the nano nature of chitin nanofibers plays an important role in the antifungal activity against Aspergillus niger.

Heterogeneously Catalysed Mild Hydrogenolytic Depolymerisation of Lignin Under Microwave Irradiation with Hydrogen‐Donating Solvents

A series of hydrogen‐donating solvents have been investigated in lignin depolymerisation practices by using a mild, microwave‐assisted, hydrogen‐free, hydrogenolytic approach promoted by the use of in situ hydrogen generating reagents with Ni 10 % Al‐SBA‐15 as a heterogeneous catalyst. Selected solvents were tetralin, isopropanol, glycerol and formic acid. Final identified products, namely bio‐oil, biochar and residual lignin were characterised by using GC–MS, matrix‐assisted laser desorption/ionisation time‐of‐flight mass spectrometry and high‐performance size‐exclusion chromatography to evaluate the extension of the hydrogenolytic process. Interestingly, the obtained phenolic monomeric products were found to be remarkably affected by the type of hydrogen‐donating solvent, with the best results obtained with formic acid, a potentially renewable derived solvent, which unexpectedly provided no biochar as compared to a maximum of 38 % obtained for tetralin. The reported protocol constitutes another step towards the development of fully sustainable and “green” methodologies of low environmental impact for lignin depolymerisation.

Fractionation of organosolv lignin from olive tree clippings and its valorization to simple phenolic compounds.

Lignin valorization practices have attracted a great deal of interest in recent years due to the large excess of lignin produced by the pulp and paper industry, together with second-generation bioethanol plants. In this work, a new lignin valorization approach is proposed. It involves ultrafiltration as a fractionation process to separate different molecular weight lignin fractions followed by a hydrogen-free, mild, hydrogenolytic, heterogeneously catalyzed methodology assisted by microwave irradiation to obtain simple phenolic, monomeric products by depolymerization using a nickel-based catalyst. The main products obtained were desaspidinol, syringaldehyde, and syringol; this proves the efficiency of the depolymerization conditions applied. The concentration of these observed compounds increased when the molecular weights of the lignin fractions increased. The applied depolymerization conditions, which take advantage of the use of formic acid as a hydrogen-donating solvent, did not generate any biochar in the systems.

Effect of mass transfer kinetics on the performance of adsorptive heat pump systems

The performance of adsorptive heat pump systems is affected by both heat and mass transfer kinetics. The present paper addresses the effect of intraparticle mass transfer limitations. Three models are used to describe refrigerant transfer between gaseous and solid phases, namely, the equilibrium, the solid diffusion and the linear driving force models. It is shown that in the case where the intraparticle diffusional resistances are significant, the system performance is markedly decreased. Moreover, the use of a linearized adsorption rate expression outside its domain of validity can produce erroneous numerical simulations.

Autohydrolysis and organosolv process for recovery of hemicelluloses, phenolic compounds and lignin from grape stalks.

A combination of two environment-friend processes for hemicelluloses and lignin recovery from red grape stalks were investigated: an autohydrolysis pretreatment at 180°C for 30 min followed by a non-catalysed ethanol organosolv step at 180°C for 90 min. Hemicelluloses were precipitated by ethanol addition to autohydrolysis liquor, while lignin was tentatively precipitated by acidification of liquors from both the processes. Results suggest that stalks hemicelluloses can be easily hydrolysed requiring a milder treatment to reduce sugar degradation, while the organosolv process did not give a consistent delignification. Autohydrolysis allowed a recovery of 2% (on stalks d.m.) of total phenols in the liquor. Organosolv liquor had a higher concentration of phenols (corresponding to 0.72% of stalks d.m.) which almost completely precipitated with lignin.

Lignin oxidation and depolymerisation in ionic liquids

The depolymerisation of lignin directly in the black liquor was studied, comparing two ionic liquids as extracting solvents (butylimidazolium hydrogen sulphate and triethylammonium hydrogen sulphate), under oxidising conditions. H2O2 was chosen as the oxidant agent. It was observed that lignins derived from butylimidazolium hydrogen sulphate were more susceptible to degradation. The main degradation products found in the extracted oils were aromatic acids, such as vanillic acid, benzoic acid and 1,2-benzenedicarboxylic acid.

Self-bonded composite films based on cellulose nanofibers and chitin nanocrystals as antifungal materials.

Cellulose nanofibers and chitin nanocrystals, two main components of agricultural and aquacultural by-products, were obtained from blue agave and yellow squat lobster industrial residues. Cellulose nanofibers were obtained using high pressure homogenization, while chitin nanocrystals were obtained by hydrolysis in acid medium. Cellulose nanofibers and chitin nanocrystals were characterized by X-ray diffraction, Atomic Force Microscopy and Infrared spectroscopy. Self-bonded composite films with different composition were fabricated by hot pressing and their properties were evaluated. Antifungal activity of chitin nanocrystals was studied using a Cellometer(®) cell count device, mechanical properties at tension were measured with a universal testing machine, water vapor permeability was evaluated with a thermohygrometer and surface tension with sessile drop contact angle method. The addition of chitin nanocrystals reduced slightly the mechanical properties of the composite. Presence of chitin nanocrystals influenced the growth of Aspergillus sp fungus in the surface of the composites as expected.

Corncob arabinoxylan for new materials

Corncob agricultural waste was used as a source of arabinoxylan for preparation of films. Three arabinoxylan samples were prepared: crude extract (CCAX), purified by a washing step, and purified by bleaching CCAX. Films prepared with untreated CCAX were water soluble, yellowish in color and had poor mechanical properties. After the purification processes the Youngs modulus increased from ∼ 293 MPa to ∼ 1400-1600 MPa, and strength was improved from ∼ 9 MPa to around 53 MPa, while the strain at break was kept at ∼ 8% both in untreated and purified CCAX. The contact angle was increased from ∼ 21.3° to 67-74° after washing or bleaching CCAX. Acetylation of bleached CCAX showed the highest thermal resistance (325 °C), had low Tg (125°C) and a high contact angle (80°), and its films were stronger (strength ∼ 67 MPa; Youngs modulus ∼ 2241 MPa) and more flexible (∼ 13%). These characteristics make purified CCAX a suitable material to be used as a matrix for film applications.