Non-food Crops-to-Industry schemes in eu27”

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2.4 Lignin

The word lignin is derived from the Latin word lignum meaning wood. Lignin is derived from trees, plants, and agricultural crops that are an abundant and renewable resource. It is a naturally occurring aromatic polymer that comprises between 20 and 35% of all perennial land-growing plants. Lignin is deposited by plants when they experience the need for developing (a) a water-conducting cell system, (b) the mechanical support for a solar energy collecting crown, and (c) a decay-resistant mature tissue (xylem). Lignin serves the tree as sealant, as fiber-bonding matrix and adhesive, and as antioxidant. Lignin is formed biosynthetically at the end of the life cycle through the lignifictation process.

Lignification (i.e., polymerization of precursors) progress is implemented from the cell corners to eventually form a continuous matrix throughout the tree or plant. It is confined to locations outside of the cytoplasm. Lignin is formed by the involvement of one or several extracellular enzymes that set in motion a more or less random free-radical polymerization of phenolic repeat units (so-called “lignols”). These lignin precursors are presented in the following figure 9 and they are: p-coumaryl (I), coniferyl (II) and sinapyl (III)) This reaction is an enzyme-initiated dehydrogenative polymerization that yields in the amorphous structure of lignin.

Figure 9. Chemical structures of three alcoholic precursors of lignin

The amount of lignin in plants varies widely according to the kind of plant. However, in the case of wood, the amount of lignin ranges from 19 – 30%, and in the case of non-wood fibre, ranges from 8 - 22% when the amount is determined according to Klason lignin analysis which is dependent on the hydrolysis and solubilization of the carbohydrate component of the lignified material, leaving lignin as a residue.

In addition to differences between lignins in native plant tissue, lignins also vary in relation to their method of isolation. Whereas lignins isolated by means of aqueous alkali (often in the presence of reducing sulfur compounds as during kraft pulping) typically are high in phenolic OH content and low in ether bonds. Lignins isolated under acidic conditions, in the presence of sulfite ions (as during sulfite pulping), typically are lower in phenolic OH content and higher in alkyl-aryl ether bonds. In addition, isolated lignins often have functional groups and substituents that were introduced during the process of isolation, and that are absent in native lignin.

Today, only 1-2% of overall lignin is utilized for value added applications while the remaining material is primarily used as bio-fuel [24].

The commercial available lignin comes mainly from the industrial pulp and paper processes and is known as “kraft” lignin (with SH groups) or lignosulfonates (with SO3-groups). Experimental and/or pilot plant lignins are also available from “organosolv” process (use of aqueous ethanol for delignification), and from “steam explosion” (use of high-pressure steam followed by sudden decompression and lignin extraction). At lab scale some more processes are also available.

Physical and chemical properties of lignin depend on the extraction technology. For example, lignosulfonates are hydrophilic (will dissolve in water) and kraft lignins are hydrophobic (will not dissolve in water). Isolated lignins are dark brown-colored powders that often resist thermal softening, as well as dissolution in organic solvents. Chemical modification, has been demonstrated to be a useful technique for improving lignin's handling characteristics. Lignin esters and ethers have been prepared in the laboratory, and they have been shown to possess significantly improved thermal, solubility, and molecular weight characteristics. Lignin esters and hydroxy alkyl ethers have been the subject of extensive investigations in both thermoplastic and thermosetting polymer systems.

A few of the current uses of lignin are summarized in the following table 1.

Table 1: Indicative uses of lignin

Many thermoplastic and thermosetting polymer systems have been benefited from the incorporation of lignin in the form of filler.

In thermoplastics, the addition of lignin and thermoplastic lignin derivatives to polyethylene and ethylene-vinyl acetate copolymers has produced evidence for the capacity of lignin to form polyblends in which the phase morphology is dictated by secondary (hydrogen) bonds. Blends of lignin and lignin derivatives have been reported with poly(vinyl alcohol), poly(vinyl acetate), polyethylene, poly(ethylene-co-vinylacetate), poly(methyl methacrylate), poly(caprolactone), polystyrene, poly(vinylchloride), and cellulose ethers and esters. Star-shaped copolymers of lignin with caprolactone had remarkable phase compatibility with poly(vinyl chloride).

The interaction of lignin and lignin derivatives with cellulose and cellulose derivatives demonstrated partial miscibility and the formation of a well-mixed amorphous phase.

Transformation of lignin by chemical modification into star-like copolymers with aliphatic ethers, aliphatic esters (caprolactone), or cellulose ester blocks produced low molecular weight, thermoplastic substances on lignin basis with excellent processing characteristics, and with phase behaviour ranging from the highly compatible to the highly incompatible.

Polyurethanes and polyamines resulted from the crosslinking of hydroxyalkyl lignin derivatives with diisocyanates and melamine, respectively.

Polyacrylates on lignin basis were formed from acrylated lignin derivatives.

Cured epoxy systems resulted from both carboxylated lignins crosslinked with multifunctional oxiranes, and from glycidyl ether-modified lignins crosslinked with diamines or anhydrides of dicarboxylic acids.

Lignin finds also application in the synthesis of thermosetting polymers that are the ones mostly used as adhesives in the wood-based industry. Lignin-filled thermosets, especially phenolic resins and reinforced rubber formulations, benefit from lignin's glassy (i.e., high modulus) nature.

In order to include lignin more effectively in network structures, some chemical modifications have been employed like hydroxymethylation (methylolation) of lignin with formaldehyde, glyoxalation of lignin with glyoxal and phenolation with phenol. Lignin is allowed to react firstly with any of formaldehyde, glyoxal or phenol and then it is used in condensation reactions. Other interesting binding systems reported in the literature include adhesive produced by the reaction of lignin with tannin and furanic compounds (furfuryl alcohol)

Phenolation (or phenolysis) is mostly applied to the lignin derived as waste of the pulp and paper industry where it is available in large amounts of low cost but it has extremely low reactivity. The direct use of such lignin as a phenol substitute would require very long press times and temperatures and therefore it is not commercially attractive [25]. Thus, there is considerable interest to process lignin prior to resin synthesis [26, 27] to produce more reactive phenolic precursors suitable to be used either as filler or as a phenol substitute in phenol-based resins.

Phenolated Organosolv Alcell lignin is also referred in the literature as phenol substitute in PF resins [28]. The lignin phenol formaldehyde (LPF) resins exhibited adequate properties such as a curing time and viscosity comparable to those of standard commercial PF resins. These resins had up to 30% phenol substituted with the phenolated lignin and demonstrated similar physical and mechanical properties as for standard PF resins. They were successfully tested on particle boards [29].

Sulphur-free lignin extracted from steam exploded white birch pulp was reacted with formaldehyde after phenolysis to produce a renewable phenolic resin [30]. This steam explosion lignin based resin had intrinsic retardation in curing behaviour as compared to a commercial phenolic resin which might be due to its low pH value. Once cured, it had excellent bond strength, comparable to standard phenolic resins.

Lignin originated from sugarcane bagasse has been evaluated with regard to the possibility of developing renewable wood adhesives [31]. It was suggested that bagasse lignin has a high number of hydroxyl groups per phenyl-propane unit and hence might have particularly promising potential as a source of phenolic precursors. LPF resins were characterised and tested on specimens prepared from a teak wood–teak wood interface. The results indicated better bonding strength than for the standard PF resin at a phenol substitution level of 50%. Characterisation of the LPF resins demonstrated their structural similarity to the standard resin. It also showed relatively lower thermal stability and temperature required for curing the resins.

Although lignin polymers have been studied for many years now, only few processes have been transferred to industrial scale. In particular, the company Lenox Polymers Ltd., in Port Huron, Michigan, has developed and commercialized the technology to produce specialty resins from lignin as a replacement for various petrochemical polymers currently being used in the adhesive and plastics industry (Lenox Polymers Ltd. 2000). In Canada, Lenox is traded under the symbol LENP.

A German company called Tecnaro has been producing a lignin-based high quality thermoplastic (sold under the name Arboform) on a commercial scale since 2002, when they produced close to 300 tonnes. In 2002, the price of their product was US$5.50/kg, but as demand for this type of plastic increases, and production increases proportionately, prices will decline, making the plastic a more feasible alternative. Tecnaro is currently using the lignin-based polymer to manufacture watches, figurines and flashlight handles. Other applications are automotive parts that look like wood but don’t warp or crack.

Today the market is dominated by the lignins derived as co-products of the chemical pulping processes for the production of paper (kraft and lignosulfates). The demand for this type of lignin is expected to continue to grow as industries search for cheaper and more environmentally friendly sources of raw materials. The pulp and paper industry sells 1 million tonnes of lingosulfonates annually, making it the largest commercial source of lignin products

2.5 Bio-liquid from biomass

Biomass is made up of three main components: hemicellulose, cellulose anAs already mentioned before lignin is of particular interest due to its phenolic nature from which a wide variety of phenols and phenol derivatives and aromatic chemicals can be derived which can replace phenol in the formulation of adhesives.

The phenol-based resins may be prepared utilising as raw materials either the whole liquid product or a fraction enriched in phenolics that obtained from the thermal conversion of biomass after fractional condensation or further processing.

The main thermal conversion methods used are:

  • fast pyrolysis

  • vacuum pyrolysis

  • pressure liquefaction

Forestry and agricultural biomass has been tested as feedstock for the production of reactive phenolic compounds using any of the above thermal conversion methods.

Each method results in materials with varying properties and thus they are mentioning separately.

2.5.1 Fast pyrolysis

Fast pyrolysis is a relatively recent thermochemical conversion technology where biomass is treated at temperatures between 400 and 600oC for very short time. This method gives very high liquid yields, up to roughly 75 wt% on a dry basis.

Pyrolysis oils are a complex mixture of water, higher molecular weight lignin fragments and lower molecular weight organics. Water is the most abundant compound, typically followed by hydroxyacetaldehyde (up to around 10 wt%), and acetic and formic acid (up to around 8 wt%). Bio-oil compounds have been classified into the main categories of hydroxyaldehydes, hydroxyketones, sugars, carboxylic acids and phenolics while the concentration of phenol itself is typically very low (appx. 0.1%). Bio-oil compounds can be separated according to their water solubility. The majority of the water-insoluble materials are lignin-derivative compounds commonly referred to as pyrolytic lignin. Typical pyrolytic lignin yields on a wet bio-oil basis are between around 10 wt% and around 30 wt% for a wood derived bio-oil.

There are many literature references for the synthesis of adhesives based on pyrolytic bio-oil. In details:

Chum et al. [32-35] investigated pyrolysis oils derived from softwood, hardwood, and bark residue. They synthesised resins of both the novolac and resole varieties.

Direct use of fast pyrolysis oils without any product separation was evaluated by Himmelblau from Biocarbon Co. [36, 37]. Resins with a phenol substitution of 50% could still provide sufficient linkages for water resistant adhesives. These resins were said to perform nearly as well in making 3-ply plywood of southern pine as a commercial alternative.

Giroux et al. [38, 39] from Ensyn investigated a method of preparing phenolic precursors by liquefying wood, bark, forest and wood industry residues using a patented fast pyrolysis process. Ensyn’s technology has been dubbed Rapid Thermal Processing or the RTPTM process. Reactive bio-oil compounds were recovered and processed by distillation, evaporation or a combination thereof in order to obtain natural resin precursors, either as liquids or as solids [38, 39]. The reactive fraction so obtained is referred to as ‘natural resin’ and comprises a total phenolic content from roughly 30–80wt %. According to Ensyn it is a highly reactive lignin compound that has been found to be suitable for use within resin formulations without requiring any further fractionation procedure. Designed resole resins comprising up to 60% of the natural resin precursor were prepared and tested in board production and found to exhibit similar properties as those of a commercially available resin used as a control.

CHIMAR Hellas, SA [40, 41] developed Phenolic resins using whole pyrolysis oil. Phenol substitution levels of up to 50% were achieved. Compared to the synthesis of the standard resin reaction conditions had to be modified when adding bio-oil. The resole-type resin was successfully used in the production of OSB and plywood. Compared to a commercial control, it had comparable or even superior wood adhesive properties. Higher phenol substitution was considered to likely be possible with a fraction enriched in reactive phenolics. While phenol-based resins relying on naturally derived phenolics from a number of sources, for example a mixture of pyrolysis oil and/or cashew nut shell liquids (CNSL), and/or lignins [42]. The combination of at least two natural sources of phenolics resulted in a synergistic effect and enabled phenol substitution levels of up to 80%.

Pyrolysis of pine sawdust combined with condensation of vapours at different temperatures followed by a coalescing filter has been used to obtain bio oils with high selectivity of reactive compounds [32-35]. A bio-oil fraction rich in reactive phenolics was obtained from the second condenser and further treated with organic solvent and basic solutions. Between 20–25 wt% of the dry feed was recovered as phenolics and neutrals after this step. This fraction was used in Novolac and resole resin formulations. At a phenol substitution level of 50% the Novolac resin preparation had a shorter gel time than commercial plywood resins. Another important finding was the ability to reduce the amount of formaldehyde in the resin formulation, around two-thirds of the normal amount was necessary to produce a bio-oil wood adhesive with 50% phenol substitution.

Fractional condensation to produce a pyrolysis oil fraction rich in reactive phenolics for direct use in resole resins has also been evaluated [43].

Giroux and Freel [38, 39] investigated the production and use of renewable resins derived from bark and other biomass residues using rapid destructive distillation that is fast pyrolysis. Bark was pyrolysed under vacuum and the vapour condensed in stages. The resulted phenolic-rich fractions were used for the synthesis of resole resins with a phenol substitution level of 40%.

Mohan et al. [44] have reviewed fractionation processes aimed at the isolation of chemicals such as syringol or the separation of a phenolics-rich fraction, acids and neutrals from pyrolysis oils derived from a variety of biomass feedstocks and reaction conditions.

Gallivan and Matschei from American Can. Co. investigated a method of fractionating pyrolysis oils to obtain a phenolic fraction which was suitable as a total or partial substitute for phenol in making PF resins. Pyrolysis oils were obtained from the pyrolysis of wastes such as bark, sawdust, tree-tops and limbs. The phenolic fraction may be used for partial or total replacement of pure phenol in making PF resins. A resin was formulated by Gallivan and Matschei using the whole phenolic fraction, 37% formaldehyde, water and NaOH catalyst. The resulting adhesive was used to laminate veneer panels (plywood), which were tested for wood failure. The phenolic-fraction-based adhesive showed comparable results with those made from petroleum PF resin.

Separation of reactive phenols and neutral fractions through liquid–liquid fractionation in several steps has also been investigated by Chum et al. [32-35] for the preparation of PF resole resins. Preliminary results revealed that the fractionated pyrolysis oils could be used within P/F resin compositions, as P/N containing resins exhibited equivalent gel times as noted for standard P/F resins. Novolac resins and moulding compositions were also prepared with P/N fractions to substitute phenol and formaldehyde.

Pyrolytic lignins, which are considered to be the water insoluble part of pyrolysis oils, can be obtained by precipitation in water. Pyrolytic lignins are close to exclusively composed phenolic compounds. Pyrolytic lignins of pyrolysis oils precipitated from different fast pyrolysis processes have been characterised [45, 46] and found to be similar to the corresponding milled wood lignins. Most of these pyrolytic lignins are likely oligomeric alkylated aromatic units probably largely linked by C–C bonds. Scott [47] prepared pyrolytic lignins from pyrolysis oils using precipitation and centrifugation or filtration of the non-aqueous fraction. Adhesive formulations prepared using the lignins were found to be inferior to the standard P/F resin in both colour and odour, and required long press times in order to avoid de-lamination of wafer-boards. Tests indicated that none of the pyrolytic lignin samples met the internal bond (IB) test requirement.

2.5.2 Vacuum pyrolysis

In addition to fast pyrolysis, vacuum pyrolysis has been investigated as a means of producing phenolic resin precursors from lingo-cellulosic materials. Compared to fast pyrolysis, longer residence times are employed.

Roy et al. [43] investigated the production of a phenolics-rich pyrolysis oil for direct use in making resole resins. A resole resin prepared from the phenolics-rich pyrolysis oil with 40% phenol substitution and was used for the manufacture and evaluation of OSB panels. Mechanical properties (i.e. IB, torsion shear) were superior to those of the control panels prepared with a commercial resin [48].

Amen-Chen et al. [49] evaluated vacuum pyrolysis oils as phenol substitutes for resole type resins. The pyrolysis oils reacted with formaldehyde during resin synthesis and no separation or fractionation processes were required except for the removal of low molecular weight organic acids. As a feedstock, softwood bark from balsam fir, white spruce and black spruce, was used and yielded 28wt% of oil, 27 wt% of char, 17wt% of gas and 25 wt% of pyrolytic water. The technology is known as the Pyrocycling process and was commercialised by Pyrovac Inc. [43]. Resole resins were prepared at petroleum phenol replacements of 25 and 50 wt% using the bark derived oils with formaldehyde to phenol ratios of 2.25, 2.0 and 1.75. Strandboards manufactured with the resins exhibited mechanical properties such as modulus of rupture, modulus of elasticity and internal bonding better than those specified in the Canadian Standards. The thickness swelling test of the boards did not meet the standards. The resins having 25 wt% phenol replaced by pyrolysis oils were found to be suitable as surface resins and the performance was comparable to that of the commercial resin. Substitutions of up to 50 wt% of phenol with the pyrolysis oil reduced the crosslinking of the resin which was evident in lower internal bonding properties. The resins showed slower curing kinetics and lower thermal stability than those of the commercial control [50]. A small concentration of polypropylene carbonate (0.5–1.5 wt%) was added to the wood adhesives to improve the curing behaviour. However, addition of polypropylene carbonate did not significantly improve the mechanical properties of strandboards [51].

2.5.3 Pressure liquefaction

Liquefaction of lingo-celullosic materials represents another route for obtaining phenolic resin precursors. It is generally performed under high pressure at temperatures of <350oC and followed by a separation process. The ultimate pH of liquefaction is always acidic whether the starting pH is alkaline or acidic. Wood, particularly waste hard wood (birch), is more susceptible to liquefaction than other biomass feedstocks [52]. Synthesis of phenolic resins was performed by direct reacting of phenolics fraction with 37% formaldehyde solution, water and NaOH catalyst. The phenolic resin was tested on birch veneer plywood. A better bond strength was achieved than for the commercial control.

Liquefaction of corn bran was evaluated for the production of a resole-type resin [53]. The methanol-soluble fraction was analysed and also used as a phenolic resin precursor. For the resole resin synthesis, the liquefied oil derived from corn bran was mixed with 37% aqueous formaldehyde and sodium hydroxide, then refluxed at 55–85oC for 1–4 h. Mild condensation conditions were preferred to prevent the formation of high molecular weight compounds and the consequent deterioration of resin viscosity. The properties of this resole resin namely gel time and viscosity were comparable to those of a conventional resole resin.

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