Lignin as a base material for materials applications: Chemistry,application and economics

Lignin has long laboured under the label of “waste material”. However, as part of the thematic network EUROLIGNIN, a survey and desk study was undertaken to assess the changes and patterns in the utilisation of lignin with respect to materials applications. This showed that over the last 10–15 years there has been an explosion of research into, and commercialisation of, lignin-based products and processes which add significant value to a material that was previously, and continues to be, used as a low-value fuel for pulping boilers. The innate chemistry of lignin, a phenolic heteropolymer, has allowed it to make inroads into the high value polymer industries whilst continuing to act as feedstock material for the binder industries. Indeed the replacement of phenolics by lignin in resins systems is economically attractive with the phenolic resins market utilising approximately 2.52 M tonnes in 2001. Currently lignin, predominantly as lignosulphates, is used as a binding and dispersing agent in different industries with approximately 1 M tonnes (on a 100% solids basis) used annually, for example, in concrete admixtures. These and other applications will be discussed and expanded upon here with emphasis on both the economics of the markets and what is still required for lignin to mature as a valuable resource in its own right.     

Kinetics of organosolv delignification of fibre crop Arundo donax L

Kinetics of ethanol–alkali delignification of fibre crop Arundo donax L. (giant reed) has been studied. The improved approach for determination of the reaction rate constants by accurate quantification of lignin fractions with different reactivity during standard procedure of graphical differentiation was applied. Following to a simplified model, the delignification process was considered as a complex of n-parallel irreversible first-order reactions with similar final product and analysed as a multi-component reaction system. Three kinetically distinguishable lignin fractions of A. donax were revealed and quantified in proportion of approximately 61, 23 and 16% (as initial, bulk and residual lignin, respectively) and their effective degradation rate constants were determined for different pulping conditions. The proportion of lignin fractions was different from that reported for wood, but close to another crop—wheat straw, where the initial lignin fraction was also found as a major fraction (about 90%). The values of apparent activation energy were estimated respectively as 64, 89 and 96 kJ mol⁻¹, and were generally within the range of those reported for wood kraft and organosolv pulping. The simulation of ethanol–alkali delignification using found kinetic parameters showed the high reproducibility of experimental data on lignin removal, providing thereby the adequate test on validation of the suggested kinetic approach. The data reproducibility was substantially higher in comparison with conventional consecutive kinetic model (sum of square residuals (SQR) 0.0036 versus 0.0856).     

Multivariate chemometric analysis of the fluorescence spectra of eucalyptus wood

In this paper, multivariate chemometric analysis of fluorescence spectra of juvenile and mature eucalyptus wood samples is used in order to investigate the existence of any correlation between fluorescence data and, the physical/chemical properties, as well as the pulping data of eucalyptus wood. The results obtained demonstrated that the wood of juvenile and adult trees could be discriminated by fluorescence spectroscopy. Data analysis also has shown the existence of good statistical correlation between fluorescence data on the one hand, and ash content, sodium hydroxide solubility, and lignin monomeric composition of the wood samples on the other hand. Moreover, fluorescence spectral data were found to be well correlated with the pulping yield and the Kappa number of the kraft pulps issued from the adult and juvenile eucalyptus wood.     

Comparison of various pulping processes for producing pulp from vine shoots

The results of characterization for four different vine shoot varieties, grown using two different methods, revealed no significant differences in composition among vine varieties or between growing methods. The holocellulose content of vine shoots (67.14%) is lower than those of other non-wood raw materials (e.g. wheat straw, sunflower stalks, cotton stalks, etc.), but similar to those of pine and higher to those of olive trimmings. On the other hand, their lignin content (20.27%) is similar to those of eucalyptus and the non-wood raw materials. Also, their contents in cold-water, hot-water and 1% soda solubles, and ethanol–benzene extractables, are higher than for pine and eucalyptus.Soda, kraft, ethanol and ethylene–glycol pulping processes have low yields (29–47%) relative to the pulping processes applied to olive trimmings and wheat straw. Kraft pulp is that exhibiting the best properties, including a higher α-cellulose content (73.74%) than pulp from wheat straw or olive trimmings, but a higher lignin content (17.18%). Also, kraft pulp provides paper with the highest breaking length, burst index and tear index (viz. 1316 m, 1.63 kN/g and 1.59 mN m²/g, respectively); these values, which are intermediate among those for olive trimmings, wheat straw and sunflower seeds, are low and can be substantially improved by appropriate refining of the pulp.     

Chemical composition of grape stalks of Vitis vinifera L. from red grape pomaces

The chemical composition and the structure of macromolecular components of grape stalks from red grape pomaces have been evaluated. These are composed mainly of cellulose (30.3%), hemicelluloses (21.0%), lignin (17.4%), tannins (15.9%) and proteins (6.1%). Among hemicelluloses the xylan was the most abundant (ca. 12%). The parameters of cellulose unitary cell, average diameter of nanofibrils and the degree of crystallinity (75.4%) were assessed by X-ray scattering analysis. The xylan was partially acetylated glucuronoxylan (DS = 0.49) possessing the Xylp:MeGlcpA ratio of 25:1. The lignin of grape stalks was suggested to be of HGS type with H:G:S molar proportion of 3:71:26 as revealed by analysis of nitrobenzene oxidation products. Among alkali soluble condensed tannins procyanidins prevailed over prodelphinidins. The abnormal response of grape stalks to kraft pulping, leading to poorly delignified fibrous material, was attributed to a particular lignin structure and it structural association with other macromolecular components of grape stalks.     

Pulp from oil palm fronds by chemical processes

To enhance the use of the abundant biomass generated by the palm oil industry in Malaysia a study was conducted in view of exploring the papermaking potential of this industrial byproduct. Fiber strands from the frond of oil palm trees were examined relative to their physical and chemical characteristics and their response to chemical pulping such as sulfite, soda-sulfite and soda processes. Morphologically, the frond fibers are comparable to those of hardwood. They contain high content of holocellulose but low in lignin. Chemical pulps of 45–50% yield produced either by soda-sulfite or soda process exhibit acceptable papermaking properties comparable to those of hardwood kraft pulps. The study showed that frond pulp might be used as a reinforcement component in newsprint production using softwood thermomechanical fibers.     

Characterization of three non-product materials from a bleached eucalyptus kraft pulp mill, in view of valorising them as a source of cellulose fibres

This paper is a contribution of scientific knowledge on the characteristics of several by-product materials from a bleached eucalyptus kraft pulp mill. In fact, three industrial wastes arising from bleached hardwood kraft pulps, namely: unbleached screen rejects (USR), effluent treatment (ETW), and eucalyptus bark (EB) were analyzed with the aim of their possible valorization as an alternative source of cellulose. Pure powder cellulose, CEAL, from Aldrich was also analyzed, as a reference. The structural, thermal, and morphological study of these raw materials were carried out by Fourier transform infrared spectroscopy (FTIR), energy dispersion spectrometry (EDS), X-ray diffraction (XRD), thermogravimetry (TG), temperature modulated differential scanning calorimetry (TMDSC) and scanning electron microscopy (SEM). Their morphological properties were determined using MorFi apparatus. For this study the sample bleached kraft pulp, BKP, was analyzed as a reference. Lignin and carbohydrate contents were also quantified. These by-products were studied as such (i.e. without careful purification) because we intended to find rational and low-cost way of valorization. In fact any additional operation will induce an over cost. The results obtained indicate that these industrial wastes can be potential raw material in fibre-based applications (paper, composites, …), since they contain a high proportion of cellulose with preserved fibrillar morphology and good thermal stability. Some of these materials have low lignin and inorganic residue contents.     

Evaluation of grape stalks as a bioresource

The compositional characteristics of grape stalk in terms of lignin, sugars, ash, extractives and tannins contents were established. The biomass composition of grape stalk is 34% lignin, 36% cellulose, 24% hemicellulose and 6% tannins. The tannins, analysed by solution ¹³C NMR, were essentially of procyanidin type and the dichloromethane extractives fraction, characterized by GC-MS, was mainly composed of fatty acids. Different processes for the pretreatment of grape stalk were compared. Due to the high content of lignin and tannins, dilute sulfuric acid and ethanol organosolv pretreatments resulted in a low degree of delignification. However, a wet oxidation process permitted a significant reduction of the Klason lignin content of the pulp with a good carbohydrate recovery and improved enzymatic digestibility.     

Lignin based controlled release coatings

Urea is a commonly used fertilizer. Due to its high water-solubility, misuse easily leads to excess nitrogen levels in the soil. The aim of this research was to develop an economically feasible and biodegradable slow-release coating for urea. For this purpose, lignin was selected as coating material. From four commercially available lignins, two lignosulfonates (Wafex P and Borresperce), a softwood kraft (Indulin AT) and soda flax lignin (Bioplast), the latter showed the best potential with respect to film forming properties.Bioplast dispersions up to a dry matter content of 50% are processable. However, high losses during processing resulted in thin coating layers on the urea granules. To reduce urea release, hydrophobic compounds and crosslinkers were added to the Bioplast dispersions. Addition of alkenyl succinic anhydride (ASA) significantly decreased the release of urea in water. However, complete release of urea still occurred within one hour, which can be explained by a low reactivity of the selected compounds towards lignin, too low percentages of applied coating or negative effects of the selected compounds on the film forming process. In addition, urea partly dissolves in the aqueous lignin dispersions due to its high water-solubility. This causes incorporation of urea in the lignin layer, which results in coatings with a low water resistance. This was improved by application of an inner coating layer with high dry matter content.In conclusion, lignin shows high potential as coating material. For industrial application, more insight in the film forming properties is desired.     

Chemical composition and pulp characterization of Tunisian vine stems

In this study, the valorisation of Tunisian vine stem wastes was investigated. The chemical composition of the vine stems was studied, and it was found that when compared to non-wood plants, they contain greater amounts of extractives, lignin, and comparable holocellulose content. An elementary analysis of the ashes showed that the major constituents were mineral elements (K and Ca). Soda pulping of vine stems led to a yield of about 35% after the bleaching step. This amount is lower than that obtained for wood plants and similar to that observed for annual plants. The morphological properties, Kappa number, and degree of polymerization of the resulting pulp were determined. Finally, paper handsheets were prepared from the pulp, and their physical properties were investigated. The breaking length, Young's modulus, and burst index of the produced paper presents quite acceptable values. Further, the silica content of the stems is low, which is advantageous for the pulping process. Experimental results obtained for both the pulp and paper show that this agricultural residue has the potential to be used for papermaking applications.     

Structural characterization of stalk lignin from banana plant

Dioxane lignins from two fractions of banana plant ‘Dwarf Cavendish’ stalk (floral stalk (DL_FS) and rachis (DL_R)) were structurally characterized by a set of spectroscopic (Ultraviolet (UV), FTIR, solid- and liquid-state NMR) and chemical degradation (permanganate (PO) and nitrobenzene oxidation (NO)) techniques. Despite both lignins are of HGS-type, strong structural differences were observed between them. Thus, DL_FS showed almost twice the abundance of H and G units and almost half of the abundance of S units when compared to DL_R. DL_R possessed significantly higher amount of β-O-4′ structures (0.32/C₆ against 0.12/C₆) and the molecular weight (5400 Da against 3750 Da) than those of DL_FS. About 72% of the condensed structures in DL_FS are of β-5 and 5–5′ types, whereas 4-O-5′-diaryl ether structures were the most abundant condensed structures in DL_R. Most of H units in both lignins are terminal phenolic coumarates linked to lignin substructures by ester bonds. Both lignins are structurally associated with suberin-like components in cell wall tissues. Structural features of stalk lignin were discussed in terms of possible restrictions for the kraft pulping of integral stem material.     

Applicability of lignins from different sources as antioxidants based on the protective effects on lipid peroxidation induced by oxygen radicals

Increasing evidence suggest that excessive concentrations of reactive oxygen species in the human body are involved in a number of pathological events and that oxidative damage to cell components may play an important pathophysiological role in many types of human diseases. Several studies have shown the possible benefits of antioxidants from plant sources in altering, reversing or forestalling the negative effects of oxidative stress.The study was designed to evaluate whether lignins prevent H₂O₂-induced lipid peroxidation. The protective effect of industrial lignins obtained from different sources against hydrogen peroxide induced oxidation was investigated in normal human red blood cells (RBCs). RBCs, preincubated with different amounts of lignins and challenged with hydrogen peroxide were analyzed for lipid peroxidation. The high molecular weight can be considered as one of the main factors decreasing the radical scavenging activity. When comparing different lignins the inhibitory effects against lipid peroxidation were notably related to their molecular weights. In this sense bagasse with the lowest Mn was the greatest antioxidant and lignosulfonate with the highest Mn was the lowest antioxidant lignin.These results open the possibility of new applications of lignins. The potential health benefits and industrial applications of lignins make them a promising research resource.     

Cynara cardunculus L. — a new fibre crop for pulp and paper production

The pulping potential of the thistle Cynara cardunculus L. was evaluated by studying anatomy and chemical composition of the stalks and Kraft pulp yields and properties. C. cardunculus is a perennial plant, with annual harvests, that can be grown in hot and dry climates with high productivities. The stalk of the plant has a central pith, ca. 45% in volume and 10% in weight, of small parenchyma cells, surrounded by a cortex where numerous fibre vascular bundles are imbedded. The fibres are on average 1.3 mm long, 18.8 μm wide and have a 4.8 μm wall thickness. The whole stalks have 7.7% ash, 14.6% extractives, 17.0% lignin and 53.0% polysaccharides, mainly cellulose and xylans. The pith has more lignin than the depithed stalk (20.3 vs. 13.6%). The Cynara stalks could be cooked by standard Kraft pulping to produce well delignified pulps with high yields (44–47% with Kappa 11–15), low rejects and very good strength properties, especially in relation to tensile strength. Depithing of the stalks has a positive impact on pulp yield, chemical consumption and on the pulp strength properties.     

Pulp and paper from kenaf bast fibers

Samples of kenaf (Hibiscus cannabinus) grown in Malaysia were examined to determine the kraft pulp and papermaking properties of their bast (or bark) fibers. Using kraft pulping process showed that bast fibers were relatively easy to cook resulting good pulp yields in the range of 45–51%. The bast pulp produced sheets with great density, tear index and dry zero-span breaking length. Kenaf bast fiber is considered promising for production of high-grade printing, writing and specialty papers.     

Studies on Hibiscus cannabinus and Hibiscus sabdariffa as an alternative pulp blend for softwood: An optimization of kraft delignification process

Hibiscus cannabinus and Hibiscus sabdariffa, agro-based residues consist of bast and wood fibers which resemble to those of softwood and hardwood, respectively. The runkel ratio of core fibers H. cannabinus and H. sabdariffa is comparable to that of Picca abies, whereas, it is much less than those of hardwood like Eucalyptus tereticornis. The slenderness ratio of H. cannabinus is much closer to P. abies in comparison to H. sabdariffa whereas, it is 7.7 and 13% less than E. tereticornis. The flexibility coefficient of H. cannabinus and H. sabdariffa are slightly lower than that of P. abies but it is 59.6 and 57.0% are more than that of E. tereticornis. It indicates that morphological characteristics of core fibers of H. cannabinus and H. sabdariffa closely resemble to that of softwood except fiber length which can be compensated by long bast fibers. Due to identical pulping conditions, H. cannabinus and H. sabdariffa can be delignified together by kraft pulping process. The optimum cooking conditions for H. cannabinus and H. sabdariffa were found to be as, active alkali 16%, sulfidity 20%, temperature 160 °C, time (at temperature) 120 min and wood to liquor ratio of 1:4.5. An anthraquinone (AQ) dose of 0.05% at an active alkali dose of 13% (as Na₂O) produces the screening rejects and kappa number similar to that obtained by using 15% active alkali (as Na₂O). The reaction kinetics study indicates that delignification is of first order. Low sulfidity AQ additive kraft pulping at constant H-factor produces better strength properties compared to non-additive kraft cooks.     

Improving the use of kenaf for kraft pulping by using mixtures of bast and core fibers

Kenaf (Hibiscus cannabinus L.) is a herbaceous annual plant amenable to use as a papermaking raw material. Kraft and soda pulping of kenaf have so far been done exclusively on the bark fraction (about 34–38% of the stem) or whole stem of the plant. Using kenaf bark exploits the higher quality of its bast fibers but reduces the typically high crop yields of this plant. In any case, core kraft pulp has acceptable properties some of which (e.g. tensile index, burst index) can even surpass those of bark pulp. Pulp made from both fractions has been found to exhibit better bonding properties than bark pulp. However, too high a proportion of core fibers can result in difficult drainage, a low tear strength or poor air permeability. These problems restrict the proportion of core that can be mixed with bast fibers, hinders separation of the two fractions and raises operational costs.The primary purpose of this study was to examine the influence of the core–bark ratio on the properties of mixed kenaf pulp. We used unrefined core pulp and refined bark pulp. Based on the results for kraft sacks, obtaining kenaf paper from both fractions has some advantages. Because Gurley air porosity changed dramatically with the proportion of core pulp used, it was used to determine the maximum amount of core fibers to be added to bast fibers. A proportion of up to 34% was found to have no adverse effect on air permeability. Such a proportion allowed paper strength to be preserved with an acceptable tear index (19.8 mN m²/g) and excellent tensile index (72 N m/g). Also, energy consumption was reduced if only the bark fraction was refined. The proposed strategy thus provides increased fiber yields of kenaf per hectare per year and valorizes the core fraction.     

Lignin modification improves the biofuel production potential in transgenic Populus tomentosa

Lignin has been recognized for its negative impact on forage digestibility, tree pulping properties, and cellulosic biofuel production, although it is the major structural component of the secondarily thickened cell walls of vascular plants. Earlier studies have demonstrated that lignin modification improves forage digestibility and poplar pulping properties. To determine whether lignin modification has beneficial effect on saccharification of lignocellulosic biomass, we pretreated and then enzymatically hydrolyzed the mature wood from transgenic poplar plants that expressed the antisense transgenes of monolignol biosynthesis genes 4-coumarate: CoA ligase (4CL) or caffeoyl CoA 3-O-methyltransferase (CCoAOMT). Firstly, a long-term field trial was set up for the transgenic plants. Over five years, the reduced trend of lignin content remained stable in all transgenic lines. And a total lignin reduction of up to 10% did not alter the growth rate or biomass yield of the transgenic poplars. In the mature wood, suppression of CCoAOMT increased saccharification potential, but 4CL down-regulation had no significantly positive effect on saccharification. Sugar yield were negatively correlated with soluble lignin content of dried, extractive-free stem biomass. These results imply that lignin modification can facilitate the process of saccharification for biofuel production in tree crops.     

Use of acetylated softwood kraft lignin as filler in synthetic polymers

Partially acetylated softwood kraft lignin (ASKL) is used as filler in synthetic polymers such as LDPE, PP, PS and PET. ASKL/synthetic polymer composites are prepared by melt-blending and compression molding with ASKL content up to 50.0 wt%. The chemical and physical properties of ASKL/synthetic polymer composites are also investigated. TGA results show that ASKL is more thermally stable than SKL up to 200 °C. FTIR spectra demonstrate a formation of free volume by crystallization of LDPE in ASKL/LDPE composite. DSC results show that the glass transition temperature of ASKL decreased by acetylation, and ASKL/synthetic polymer composites (50/50 w/w) have a single glass transition. The AFM images of ASKL/synthetic polymer composites show no significant phase separation. Young’s moduli of ASKL/synthetic polymer composites increased with ASKL content in some extents. Tensile strength and breaking strain of ASKL/PET composite are almost retained in spite of the addition of ASKL as a result of a contraction in free volume or densification.     

Chemical and structural characterization of lignins isolated from <Emphasis Type="Italic">Caragana sinica</Emphasis>

Successive extractions of the dewaxed Caragana sinica with 70 % ethanol, 70 % ethanol containing 1 % NaOH, 1 M KOH, 1 M NaOH, 3 M KOH, and 3 M NaOH at 75 °C for 3 h released 80.4 % of the original lignin. The physico-chemical properties and structural features of these lignin fractions were comprehensively characterized by alkaline nitrobenzene oxidation, GPC and two-dimensional NMR spectroscopy. The results showed that all the lignin fractions had relatively lower molecular average-weights ranging between 910 and 1630 g/mol. Moreover, 2D-NMR showed that the lignin fraction L₂ isolated with 70 % ethanol containing 1 % NaOH from C. sinica was similar to a hardwood lignin, with a high S/G ratio accounted for 1.2, a predominance of β-O-4′ aryl ether linkages (77 % of all side-chains), followed by β-β′ resinol-type linkages (8 %) and lower amounts of β-5′ phenylcoumaran substructures (7 %), β-1′ spirodienone-type linkages (3 %), and cinnamyl end groups (5 %). The high predominance of the S-lignin units, together with the high proportion of β-O-4′ aryl ether linkages could contribute to a relatively high reactivity of C. sinica lignin during alkaline pulping.     

Characterization of hairs and pappi from Cynara cardunculus capitula and their suitability for paper production

The capitula of Cynara cardunculus contain hairs and pappi representing 7% of the total plant biomass. These low density biomass components could be mechanically separated without apparent losses using a whole-plant processing prototype. Hairs and pappi are filamentous structures made up of longitudinally aligned fibre cells, without intercellular voids or pitting, with the following dimensions regarding length, width and wall thickness: 1.35 mm, 19.8, and 4.8 μm for hairs and 1.78 mm, 10.4, and 2.9 μm for pappi. Chemically hairs and pappi have low content of ash (1.9% and 1.1%, respectively), extractives (5.4% and 6.0%) and lignin (10.6% and 17.8%), and high content of holocellulose (77.5% and 72.8%) and α-cellulose (55.2% and 46.8%).Pulps could be produced using a conventional kraft process with high yields and low residual lignin, e.g. 63% at Kappa 7 for hairs and 48% at Kappa 11 for pappi, low coarseness values (0.04 and 0.03 mg m^?1) and adequate pulp properties for paper (40 and 42 N mg^?1 tensile index; 3.6 and 3.4 kPa m² g^?1 burst index in unrefined pulps of hairs and pappi, respectively). The results also indicated that there is scope for improving pulp quality by optimising pulping conditions to this type of new raw materials. The differences between hairs and pappi may also be further exploited namely the lower lignin content of hairs and the higher slenderness and wall thickness of pappi fibres.The utilization of hairs and pappi may strengthen the differentiated use of biomass fractions of the Cynara plant and its potential as a bioenergy crop.