Production of rayon fibres from cellulosic pulps: state of the art and current developments

The increasing demand for cellulosic fibres is continuously driven by the growing earth population and requirements of the textile industry. The annual cotton production of ca. 25 million tons is no longer enough to meet the market demands. This market gap of cellulosic fibres is progressively filled by regenerated cellulosic fibres derived from the dissolving pulp. The conventional industrial process of viscose production is far from being environmentally friendly due to the use of hazardous reagents. Alternatively, new trends in the production of regenerated fibres are related to the direct dissolution of cellulose in appropriate environmentally sound recyclable solvents, allowing high quality rayon fibres. This article reviews the sources of dissolving pulps used for the production of viscose and its quality parameters related to the performance of viscose production. The prospective cellulose regeneration processes, both commercialized and under development, are reviewed regarding current and future developments in the area.publishe

Caracterização do Engaço da Uva e Avaliação do seu Potencial como Matéria‐Prima Lenhocelulósica

Resumo O presente estudo avalia a composição química detalhada do engaço da uva de modo a encontrar novas formas para a sua valorização. O engaço da uva é um subproduto vinícola de origem lenhocelulósica, com 30-31% de celulose, 21% de hemicelulose, 17-18% de lenhina, 15-16% de taninos e cerca de 6,0% de proteínas. A análise dos monossacarídeos mostrou que, a seguir à celulose, a xilana é o segundo polissacarídeo mais abundante no engaço (ca. 12%). A celulose foi isolada pelo método Kürscher e Hoffer e foi caracterizada por difração de raios-X (DRX). Esta análise revelou a existência de uma célula unitária típica de celulose I com um elevado grau de cristalinidade (ca. 75%). Também foi possível verificar uma elevada abundância de compostos extratáveis em água (ca. 24%), atribuídos principalmente a sais inorgânicos solúveis, taninos hidrolisáveis e pectinas. A lenhina Klason foi caracterizada por espectroscopia de infravermelho e espectroscopia de ressonância magnética tendo-se verificado tratar-se de uma lenhina do tipo HGS, com predominância de unidades guaiacilo.Abstract The present study evaluates the detailed chemical composition of grape stalks to find new forms of recovery. Grape stalk is a by-product from winemaking process of lignocellulosic source with 30-31% cellulose, 21% hemicellulose, 17-18% lignin, 15-16% tannin and about 6.0% protein. Analysis of monosaccharides showed that, after cellulose, the xylan is the second most abundant polysaccharide in stalks (ca. 12%). Cellulose was isolated by the Kürscher and Hoffer method and was characterized by X-ray diffraction (XRD). This analysis revealed the existence of a typical unit cell of cellulose I with a high degree of crystallinity (ca. 75%). It was also observed a high abundance of water extractable compounds (ca. 24%), attributed to mainly soluble inorganic salts, hydrolysable tannins and pectins. Klason Lignin was characterized by infrared spectroscopy and magnetic resonance spectroscopy and it was found that this is a HGS lignin-type, predominantly with guaiacyl units

Chemical composition of different morphological parts from ‘Dwarf Cavendish’ banana plant and their potential as a non-wood renewable source of natural products

The study on chemical composition and structure of components from different morphological parts of ‘Dwarf Cavendish’ banana plant (petioles/midrib, leaf blades, floral stalk, leaf sheaths and rachis) have been carried out aiming to evaluate their potential as eventual raw materials for the chemical processing. Macromolecular components were analysed using solid-state NMR, ATR-FTIR and wet chemistry methods. Mineral components were assessed by ICP analysis of ashes obtained after raw material calcinations. It was verified that chemical composition of the studied fractions of banana plant varies significantly. The major extremes were found in the contents of cellulose (37.3% in leaf sheaths and only 15.7% in floral stalk), starch (26.3 in floral stalk and 0.4% in petioles/midrib), lignin (24.3% in leaf blades and 10.5% in rachis) and lipophilic extractives (5.8% in leaf blades and 1.2% in petioles/midrib). All morphologic parts of banana plant contained considerable amounts of ashes (from 11.6 to 26.8%) composed mainly by potassium, calcium and silicium salts. The hemicelluloses in banana plant are proposed to be mainly glucuronoxylan and xyloglucan (from 5.5% in floral stalk to 21.5% in petioles/midrib). Rather significant amount of proteins was found in leaf blades (8.3%). Lignin analysis revealed that it is of HGS type with H:G:S proportion ranged of (5–17):(18–54):(35–71). The significant variation of lignin structure among the different morphological parts of banana plant was highlighted. Results of this study allowed some propositions about possible applications of banana plant residues as non-wood renewable source of natural products.info:eu-repo/semantics/publishedVersio

Caracterização Química do Folhelho Branco e do Folhelho Tinto Proveniente de Castas Típicas da Região do Dão

Resumo O presente trabalho avalia e compara a composição química do folhelho branco e tinto, proveniente de castas típicas da região do Dão. A análise química mostra que o folhelho é constituído essencialmente por celulose, hemiceluloses, proteínas e extratáveis em água. Os compostos solúveis em água são constituídos principalmente por açúcares monoméricos (glucose e frutose) e por uma mistura complexa de hemiceluloses. A celulose do folhelho branco e tinto foi avaliada por difração de raios-X (DRX) e verificou-se que se trata de celulose I com um grau de cristalinidade de 66,1 e 72,8%, no folhelho tinto e branco, respetivamente. O teor de celulose no folhelho branco (12,5%) é bastante inferior quando comparado com o do folhelho tinto (20,8%). Os métodos espectroscópicos, nomeadamente RMN CP/MAS de 13C, permitiram verificar a presença de material ceroso e cuticular em ambos os folhelhos. Os extratáveis em diclorometano dos folhelhos são constituídos maioritariamente por ácidos gordos e terpenos.Abstract The present study evaluates and compares the chemical composition of white and red grape skins, from grapes of the typical caste Dão region. Chemical analysis shows that grape skins are constituted essentially by cellulose, hemicelluloses, and water extractable proteins. Water-soluble compounds consist primarily of monomeric sugars (glucose and fructose) and of a complex mixture of hemicelluloses. The structure of cellulose from white and red grape skins was evaluated by X-ray diffraction (DRX) and found to be cellulose I polymorph with a crystallinity degree of 66.1 and 72.8% for red and white grape skin celluloses, respectively. The content of cellulose in white grape skins (12.5%) is significantly lower when compared to that in red grape skins (20.8%). Spectroscopic methods, as 13C CP/MAS NMR, allowed the detection of waxy material in both cuticular tissues of grape skins. Dichloromethane extracts of grape skins consist mostly of fatty and triterpenic acids

Isolation and structural characterization of the acetylated heteroxylan from sisal (Agave sisalana) and its fate during alkaline pulping and TCF/ECF bleaching.

The heteroxylan from sisal, an O-acetyl-(4-O-methylglucurono)xylan with a molecular weight (Mw) of 18 kDa, was isolated by extraction of peracetic holocellulose with Me2SO and thoroughly characterized by wet chemistry, and NMR spectroscopy. The heteroxylan backbone is composed of (1→4)-linked β-D-xylopyranosyl units (Xylp) partially ramified with terminal (1→2)-linked 4-O-methyl-α-D-glucuronosyl (MeGlcpA) and a small proportion of α-D-glucuronosyl (GlcpA) residues. Roughly 61mol% of Xylp residues are acetylated (DS =0.70). During soda/AQ pulping, GlcpA and MeGlcA are partially removed or converted to 4-deoxy-β-L-threo-hex-4-enopyranosyluronic acid (HexA), though notable proportion of GlcpA maintained intact. The major part of acetyl groups was hydrolyzed during pulping. It was proposed that the predominantly low molecular weight xylan fraction was removed from pulp during bleaching. The profiles of uronosyl residues in xylans from TCF and ECF bleached sisal pulps were rather different.This study has been supported by the Spanish MEC (Project AGL2005-01748) and EU Contract NMP2-CT-2006-26456. We thank CELESA (Tortosa, Spain) for providing the samples. G.M. thanks the Spanish Ministry of Education for a FPI fellowship.Peer reviewe

Steryl glucosides from banana plant Musa acuminata Colla var cavendish

The chemical composition of the dichloromethane extracts of several vegetal fractions of banana plant, Musa acuminata Colla var cavendish have been studied by GC–MS. Several bioactive steryl glucosides, namely campesteryl 3- -d-glucopyranoside, stigmasteryl 3- -d-glucopyranoside and sitosteryl 3- -d-glucopyranoside were identified as the major components of the ex tracts, accounting for 838.4–1824.3 mg/kg of the plant fractions dry weight. The high abundance of these compounds might be an important contribution to the valorization of banana plant agricultural residues.info:eu-repo/semantics/publishedVersio

Polyoxometalates as mediators in the laccase catalyzed delignification

The polyoxometalate (POM)-laccase catalytic system was applied for the first time to aerobic delignification of kraft pulps at moderate (40-60 degreesC) temperatures. Laccase was found to readily catalyze the re-oxidation of different kinds of polyoxometalates, including those, which cannot be re-oxidized by dioxygen even at high temperatures (PMo11V1, SiW11V1. etc.). This allows a sequence of catalytic redox cycles similar to that in the laccase-mediator system (LMS) where electrons are transferred from the substrate (lignin) via POM and laccase to oxygen. Results obtained showed that the POM-laccase system could decrease kappa number of eucalypt kraft pulp from 13.7 to 8.5 though the reaction rate is relatively slow. Among different POM used, SiW11V showed the best results. The effect of the process variables on the delignification was studied. The best results in delignification of eucalypt pulp were obtained at 60 degreesC, oxygen pressure of 5 bar, pH 6.3, SiW11V concentration of 4.2 mM and laccase concentration of 0.65 U/ml. The reaction temperature appears to be one of the crucial factors in the achievement of a delignification rate acceptable for practical application. (C) 2001 Elsevier Science B.V. All rights reserved

Integrated utilization of grape skins from white grape pomaces

An approach for the integrated utilization of grape skins from white grape pomaces has been proposed. This consists of consecutive or simultaneous extraction of grape skins with neutral organic solvent and water under reflux. Organic extract is a valuable raw material for the isolation of oleanolic acid. The aqueous extract (ca 50%, w/w) is composed of essentially hexoses and suitable for the high yield (till 51%) bioethanol production at a maximum specific cell growth rate (μmax) of 0.29 h−1. The remained extracted grape skins are the complex of structural polysaccharides embedded into cutinous matrix. Extracted grape skins were shown to be a prospective raw material for the production of low-density boards (d ≤ 0.40) for insulation needs. The boards produced from grape skins and bind of 8% urea–formaldehyde resin revealed reasonable tensile strength (0.4 MPa) and a low thermal conductivity (0.09–0.12 W (m K)−1) over a wide range of temperatures (40–200 °C).info:eu-repo/semantics/publishedVersio

Structural characterization of lignin from Grape Stalks (Vitis vinifera L.)

The chemical structure of lignin from grape stalks, an abundant waste of winemaking, has been studied. The dioxane lignin was isolated from extractive- and protein-free grape stalks (Vitis vinifera L.) by modified acidolytic procedure and submitted to a structural analysis by wet chemistry (nitrobenzene and permanganate oxidation (PO)) and spectroscopic techniques. The results obtained suggest that grape stalk lignin is an HGS type with molar proportions of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) units of 3:71:26. Structural analysis by 1H and 13C NMR spectroscopy and PO indicates the predominance of β-O-4′ structures (39% mol) in grape stalk lignin together with moderate amounts of β-5′, β-β, β-1′, 5-5′, and 4-O-5′ structures. NMR studies also revealed that grape lignin should be structurally associated with tannins. The condensation degree of grape stalks lignin is higher than that of conventional wood lignins and lignins from other agricultural residues.N/

New polyoxometalate-functionalized cellulosic fibre/silica hybrids for environmental applications

Cellulosic fibre/silica hybrid materials functionalized with Keggin-type polyoxometalates ([PV2Mo10O40]52, [PVMo11O40]42, ([PMo12O40]32 or [PW12O40]32) were prepared by a sol–gel method at room temperature. The novel materials are composed of ca. 56 wt% of polysaccharides, ca. 37 wt% of propylamine-modified silica, 2 wt% of polyoxometalate, and 5% of hydration water. The silica network of these hybrids exhibits relatively high degree of condensation being distributed mainly on the surface of the cellulosic fibres as a dense film. The functionalization of silica with polyoxometalates via electrostatic interactions with protonated propylamino groups of modified silica was unambiguously confirmed. Despite their high silica content cellulose/silica hybrids retained basic cellulosic pulp properties—supramolecular and fibrous structure, porosity, relatively low density, etc. The novel bio-based material functionalized with 2% of [PVMo11O40]42 shows particularly high activity towards the oxidation of volatile organic compounds (VOCs) present in urban air thus anticipating future environmental applications.publishe