Optimal temperature conditions of carbonaceous feedstock pyrolysis

A problem of optimal control of the temperature conditions of carbonaceous feedstock pyrolysis in a plug-flow reactor was formulated, and it was shown that the optimal temperature profile depends significantly on the ratio between the activation energies of the desired and side reactions and also on the type of the main pyrolysis reactions (consecutive, parallel, or consecutive-parallel).     

Fabrication of carbon nanofiber by pyrolysis of freeze-dried cellulose nanofiber

The possibility of fabricating carbon nanofibers from cellulose nanofibers was investigated. Cellulose nanofiber of ~50 nm in diameter was produced using ball milling in an eco-friendly manner. The effect of the drying techniques of cellulose nanofibers on the morphology of carbon residue was studied. After pyrolysis of freeze-dried cellulose nanofibers below 600 °C, amorphous carbon fibers of ~20 nm in diameter were obtained. The pyrolysis of oven-dried precursors resulted in the loss of original fibrous structures. The different results arising from the two drying techniques are attributed to the difference in the spatial distance between cellulose nanofiber precursors.     

Effect of pectin extraction method on properties of cellulose nanofibers isolated from sugar beet pulp

In this study, the effect of pectin extraction method on the properties of cellulose nanofibers (CNFs) isolated from sugar beet pulp (SBP) was studied. Pectin was extracted by the industrially practiced method by sulfuric acid hydrolysis or by enzymatic hydrolysis using a cellulase/xylanase enzymes mixture. The CNFs were then isolated by high-pressure homogenization and investigated in terms of their chemical composition, crystallinity, size, degree of polymerization, and re-dispersion in water after freeze-drying. The mechanical properties and surface characteristics of CNF films were also studied. The results showed that fibrillation of the de-pectinated SBP was more efficient for the acid hydrolyzed SBP. CNFs from the acid-hydrolyzed SBP had a slightly wider diameter, higher crystallinity, viscosity, and α-cellulose content but a lower degree of polymerization than CNFs from the enzyme-hydrolyzed SBP. Owing to the presence of more residual hemicelluloses in the CNFs from the enzyme-hydrolyzed SBP, the CNFs had higher re-dispersion ability in water. CNF films from enzyme-hydrolyzed SBP displayed slightly better mechanical properties and higher water contact angle than acid-hydrolyzed CNF films.

Graphic abstract

     

Interfacial properties of cellulose nanoparticles obtained from acid and enzymatic hydrolysis of cellulose

Rod-shaped cellulose nanocrystals obtained by acid hydrolysis of eucalyptus fibers (CNCa) presented high aspect ratio (estimated length and width of 180 and 5 nm, respectively) and zeta potential of ?(17 ± 1) mV at pH 6. This typical morphology of cellulose nanocrystals was in contrast to nanoparticles obtained upon enzymatic hydrolysis of bacterial cellulose (CNCe), which were asymmetric and irregular due to surface-bound cellulases and presented a distinctive surface roughness. Interestingly, CNCe also displayed axial grooves, to yield a C-shape cross section that has not been reported before. The effect of the characteristic shape and surface chemistry of CNCa and of grooved CNCe was studied at oil/water interfaces and solid surfaces. Emulsions (20 % v/v oil) prepared with the CNCa were more stable than those prepared with CNCe, owing to their characteristic shape and surface chemistry. Hydrophilic (silica surfaces cationized by pre-adsorbed polycation) and hydrophobic (polystyrene films) solid surfaces were used as substrates for the adsorption of CNCe and CNCa for each type of surface. The ellipsometric data and AFM images indicated larger affinity of CNCe than CNCa for the hydrophobic surface. On the other hand, CNCa formed homogeneous monolayer on hydrophilic surfaces, whereas CNCe formed discontinuous films. Sequential adsorption behavior of CNCa on CNCe layers (or vice versa) suggested that the interaction between them is controlled by the orientation of enzymes bound to CNCe.     

Physical properties of TEMPO-oxidized bacterial cellulose nanofibers on the skin surface

Water-dispersed bacterial cellulose nanofibers were prepared via an oxidation reaction using 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (TEMPO) as a catalyst. It was found that TEMPO-oxidized bacterial cellulose nanofibers (TOCNs) synthesized via sodium bromide-free methods are similar to those synthesized using sodium bromide. The TOCNs retained their unique structure in water as well as in emulsion. TOCNs adhere to the skin surface while maintaining nanofibrous structures, providing inherent functions of bacterial cellulose, such as high tensile strength, high water-holding capacity, and blockage of harmful substances. When gelatin gels as model skin were coated with TOCNs, the hardness representing the elasticity was increased by 20% compared to untreated gelatin gel because TOCNs could tightly hold the gelatin structure. When porcine skin was treated with TOCNs, carboxymethyl cellulose, and hydroxyethyl cellulose, the initial water contact angles were 26.5°, 76.5°, and 64.1°, respectively. The contact angle of TOCNs dramatically decreased over time as water penetrated the fibrous structure of the TOCN film. When observed by scanning electron microscopy and confocal microscopy, TOCNs on the skin surface provided physical gaps between particles and the skin, blocking the adsorption of particulate matter to the skin surface. On the contrary, the structure of water-soluble polymers was disrupted by an external environment, such as water, so that particulate matter directly attached to the skin surface. Characterization of TOCNs on the skin surface offered insight into the function of nanofibers on the skin, which is important for their applications with respect to the skin and biomedical research.     

Characterization of the water-insoluble pyrolytic cellulose from cellulose pyrolysis oil

Water-insoluble pyrolytic cellulose with similar appearance to pyrolytic lignin was found in cellulose fast pyrolysis oil. The influence of pyrolysis temperature on pyrolytic cellulose was studied in a temperature range of 300–600 °C. The yield of the pyrolytic cellulose increased with temperature rising. The pyrolytic cellulose was characterized by various methods. The molecular weight distribution of pyrolytic cellulose was analyzed by gel permeation chromatography (GPC). Four molecular weight ranges were observed, and the M_w of the pyrolytic cellulose varied from 3.4 × 10³ to 1.93 × 10⁵ g/mol. According to the elemental analysis (EA), the pyrolytic cellulose possessed higher carbon content and lower oxygen content than cellulose. Thermogravimetric analysis (TGA) indicated that the pyrolytic cellulose underwent thermo-degradation at 127–800 °C and three mass loss peaks were observed. Detected by the pyrolysis gas chromatography–mass spectrometry (Py-GC/MS), the main pyrolysis products of the pyrolytic cellulose included saccharides, ketones, acids, furans and others. Fourier transforms infrared spectroscopy (FTIR) also demonstrated that the pyrolytic cellulose had peaks assigned to CO stretching and glycosidic bond, which agreed well with the Py-GC/MS results. The pyrolytic cellulose could be a mixture of saccharides, ketones, and their derivatives.     

Influence of pretreatment and mechanical nanofibrillation energy on properties of nanofibers from Aspen cellulose

Cellulose - The characteristics of cellulose nanofibers (CNFs) depend on many factors such as the raw material, type and intensity of the pre-treatment, and type and severity of the mechanical...     

Heterogeneity in cellulose pyrolysis indicated from the pyrolysis in sulfolane

In sulfolane (tetramethylene sulfone), which is a good solvent for the primary product, levoglucosan, cellulose is pyrolyzed completely into soluble products without forming any char. Residues during pyrolysis in sulfolane at 200, 240 and 330 °C were obtained always as colorless non-carbonized substances. From the change in the crystallinity and crystallite size as compared with the ordinary pyrolysis, a heterogeneous mechanism is indicated for cellulose pyrolysis, starting from a molecule which is less stabilized due to lack of some intermolecular interactions.     

Laser pyrolysis of carbonaceous rocks

Flash pyrolysis on carbonaceous rocks is used to determine total carbon contents as well as the state of thermal maturation of specific samples. Short, intense heating greatly accelerates maturation-like processes. A series of radical fragments are generated leaving complex char residue. These volatile fragments quench into stable molecular species, influenced by the pyrolysis environment.Experiments are described that utilize pulsed laser heating on rock samples. This convenient technique requires minimum sample preparation and is readily automated. Intense laser pulses (2–10 J) generate an acetylene-rich plasma that interacts with the normally short-lived radical fragments. During the rapid quenching process, acetylene-tagged stable compounds are formed as a direct result of acetylene-radical combination processes. Analysis of these acetylenic derivatives by gas chromatography—mass spectrometry gives a unique interpretation of both the sediment and the maturation process.     

Enzymatic hydrolysis of mannoglucans obtained from cellulose

Conclusions The mannoglucans obtained by the reduction of ketocelluloses are easily cleaved by cellulase preparations, in which connection, depending on the activity ratio of the exo and endo enzymes in the cellulase complex, the predominant hydrolysis products are either monosaccharides (glucose and mannose) or oligosaccharides, in which the residues of these sugars are connected by -(1 4) linkages.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2622–2625, November, 1979.     

Properties of cellulose micro/nanofibers obtained from eucalyptus pulp fiber treated with anaerobic digestate and high shear mixing

High production costs remain the single greatest factor limiting wider use of cellulose micro/nanofibers by industry. The objective of the present study was to investigate the potential of using a low-cost bacteria-rich digestate (liquid anaerobic digestate—AD-supernatant) on milled eucalyptus fiber followed by high-shear mixing to obtain cellulose micro/nanofibers. The morphology, crystallinity, and thermal stability of micro/nanofibers obtained by this process were studied. The bacteria population in the AD-supernatant was comprised mostly of Bacteroides graminisolvens and Parabacteroides chartae. The digestate treatment partially removed amorphous components of the pulp fiber thereby decreasing micro/nanofiber diameters and enhancing the crystalline content. The treatment also increased the size of the crystalline cellulose. The morphology and crystallinity results demonstrate the effectiveness of digestate treatments coupled with high-shear mixing as a procedure for the production of micro/nanofibers.     

Isolation and characterization of cellulose nanofibers from banana peels

Cellulose nanofibers were isolated from banana peel using a combination of chemical treatments, such as alkaline treatment, bleaching, and acid hydrolysis. The suspensions of chemically treated fibers were then passed through a high-pressure homogenizer 3, 5, and 7 times, to investigate the effect of the number of passages on the properties of the resulting cellulose nanofibers. The cellulose nanofibers isolated in this study had a dry basis yield of 5.1 %. Transmission electron microscopy showed that all treatments effectively isolated banana fibers in the nanometer scale. The micrographs of the process steps used to isolate the nanofibers revealed gradual removal of amorphous components. Increasing number of passages in the homogenizer shortened the cellulose nanofibers while furnishing more stable aqueous suspensions with zeta potential values ranging from ?16.1 to ?44.1 mV. All the samples presented aspect ratio in the range of long nanofibers, hence being potentially applicable as reinforcing agents in composites. X-ray diffraction studies revealed that homogenized nanofiber suspensions were more crystalline than non-homogenized suspensions. Fourier transform infrared spectroscopy confirmed that alkaline treatment and bleaching removed most of the hemicellulose and lignin components present in the banana fibers. Thermal analyses revealed that the developed nanofibers exhibit enhanced thermal properties. In general, the nanoparticles isolated from the banana peel have potential application as reinforcing elements in a variety of polymer composite systems.     

Study of the pyrolysis liquids obtained from different sewage sludge

Pyrolysis of sewage sludge in fluidized bed to produce bio-oil is under study as a useful way to valorise this waste. Sewage sludge is the waste produced in the wastewater treatment plants. Its composition may change due to the origin and to the non-standardized treatments in the wastewater treatment plants. The pyrolysis of three samples of anaerobically digested sewage sludge obtained from three different urban wastewater treatment plants was studied in this work. The organic and inorganic matter composition, and the volatile and ash content of these sewage sludge samples were different. The influence of these parameters on the pyrolysis product distribution and on some characteristics of these products was studied. It was determined that the ash content of the raw material had an enormous influence on the sewage sludge pyrolysis. An increase in the ash content of the sewage sludge caused an increase in the gas yield and a decrease in the liquid and the solid yield with the operational conditions studied. The increase of the volatile content of the sewage sludge samples caused an increase in the liquid yield. The H₂ proportion was the most influenced non-condensable gas. It increased significantly with the ash content. The viscosity of the pyrolysis oils decreased when the ash content augmented. On the other hand, the water content depended on the organic composition of the sewage sludge samples. The chemical composition of the pyrolysis oils was also affected by the sewage sludge ash content above all the proportion of polyaromatic hydrocarbons and nitrogen-containing aromatic compounds. These compound groups increased with the augment of the sewage sludge ash content. The oxygen-containing aliphatic compounds and the steroids decreased with the ash content, although its proportion in the sewage sludge liquid was also influenced by the organic matter composition of the sewage sludge samples.     

Effect of conditions on fast pyrolysis of bamboo lignin

Products derived from bamboo EMAL pyrolysis were investigated by means of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and the effects of temperature and catalyst (sodium chloride, permutite) on the yields of pyrolysis products were probed in detail. The results showed that thermal degradation of EMAL mainly occurred at the temperature range from 250 °C to 600 °C, and both the temperature and catalyst in EMAL pyrolysis were important factors in the formation or inhibition of products. The products that derived from p-hydroxyphenylpropanoid, guaiacylpropanoid, and syringylpropanoid of lignin units by pyrolytic reactions were classified as the heterocycle (2,3-dihydrobenzofuran), phenols, a small quantity of acetic acid and furans, etc. With an increase of pyrolysis temperature, the amount fraction of 2,3-dihydrobenzofuran (DHBF) decreased from 66.26% to 19.15%. Moreover, when the additive catalyst increased from 5% to 20%, permutite catalyst improved in the formation of DHBF from19.15% to 24.19%, whereas NaCl catalyst was effective to inhibit the production of DHBF from 19.15% to 13.08%. Permutite promoted the production of coke from EMAL pyrolysis, conversely, NaCl had an inhibiting effect on the generation of coke. And NaCl catalyst had a significant catalytic effect on raising or reducing of the product yields in bamboo lignin pyrolysis.     

Energy requirements for the disintegration of cellulose fibers into cellulose nanofibers

Cellulose nanofibers have a bright future ahead as components of nano-engineered materials, as they are an abundant, renewable and sustainable resource with outstanding mechanical properties. However, before considering real-world applications, an efficient and energetically friendly production process needs to be developed that overcomes the extensive energy consumption of shear-based existing processes. This paper analyses how the charge content influences the mechanical energy that is needed to disintegrate a cellulose fiber. The introduction of charge groups (carboxylate) is achieved through periodate oxidation followed by chlorite oxidation reactions, carried out to different extents. Modified samples are then subjected to different levels of controlled mechanical energy and the yields of three different fractions, separated by size, are obtained. The process produces highly functionalized cellulose nanofibers based almost exclusively on chemical reactions, thus avoiding the use of intensive mechanical energy in the process and consequently reducing drastically the energy consumption.     

Topochemistry of cellulose nanofibers resulting from molecular and polymer grafting

The aim of this study was to synthesize hydrophobic cellulose nanofibers (CNFs) using different chemical treatments including polymer and molecular grafting. For polymer grafting, immobilizing poly (butyl acrylate) (PBA) and poly (methyl methacrylate) (PMMA) on CNFs were implemented by the free radical method. Also, acetyl groups were introduced directly onto the CNFs surface by acetic anhydride for molecular grafting. The gravimetric and X-ray photoelectron spectroscopy analysis showed the high grafting density of PMMA on the surface of CNFs. AFM results revealed that molecular grafting created non-uniformity on the CNFs surface, as compared to polymer brushes. In addition, thermodynamic work of adhesion and work of cohesion for the modified CNFs were reduced in water and diiodomethane solvents. Dispersion factor was studied to indicate the dispersibility of CNFs in polar and non-polar media. Dispersion energy was reduced after modification as a result of decreasing interfacial tension and the dispersibility of modified CNFs was improved in diiodomethane.     

Isolation and characterization of cellulose nanofibers from four plant cellulose fibers using a chemical-ultrasonic process

Cellulose nanofibers (CNFs) were isolated from four kinds of plant cellulose fibers by a chemical-ultrasonic treatment. The chemical composition, morphology, crystalline behavior, and thermal properties of the nanofibers and their intermediate products were characterized and compared. The CNFs extracted from wood, bamboo, and wheat straw fibers had uniform diameters of 10–40 nm, whereas the flax fibers were not uniformly nanofibrillated because of their initially high cellulose content. The chemical composition of each kind of nanofibers was mainly cellulose because hemicelluloses and lignin were significantly removed during chemical process. The crystallinity of the nanofibers increased as the chemical treatments were applied. The degradation temperature of each kind of nanofiber reached beyond 330 °C. Based on the properties of the CNFs, we expect that they will be suitable for use in green nanocomposites, filtration media and optically transparent films.