Abstract
In the development of integrated biorefinery process alternatives to produce value-added by-products, various black liquors from sulfur-free pulping processes offer potential feedstocks for recovering their main chemical constituents, lignin and aliphatic carboxylic acids. In this study, lignin fractions were obtained from silver birch (Betula pendula) soda-anthraquinone black liquor by carbonation (pH to about 8.5) or by acidification (pH to about 2) with H2SO4 after carbonation or directly. These fractions were characterized by Fourier transform infrared (FTIR), ultraviolet (UV), energy dispersive X-ray fluorescence (ED XRF), and 13C nuclear magnetic resonance (13C NMR) spectroscopy. In addition, the molecular weight distributions of these lignin fractions were determined. All the experimental data clearly suggested that only small differences between the precipitated lignins existed, and thus, their equal chemical utilization seems possible.
Download PDF
Full Article
Characterization of Hardwood Soda-AQ Lignins Precipitated from Black Liquor through Selective Acidification
Hemanathan Kumar,* Raimo Alén, and Gokarneswar Sahoo
In the development of integrated biorefinery process alternatives to produce value-added by-products, various black liquors from sulfur-free pulping processes offer potential feedstocks for recovering their main chemical constituents, lignin and aliphatic carboxylic acids. In this study, lignin fractions were obtained from silver birch (Betula pendula) soda-anthraquinone black liquor by carbonation (pH to about 8.5) or by acidification (pH to about 2) with H2SO4 after carbonation or directly. These fractions were characterized by Fourier transform infrared (FTIR), ultraviolet (UV), energy dispersive X-ray fluorescence (ED XRF), and 13C nuclear magnetic resonance (13C NMR) spectroscopy. In addition, the molecular weight distributions of these lignin fractions were determined. All the experimental data clearly suggested that only small differences between the precipitated lignins existed, and thus, their equal chemical utilization seems possible.
Keywords: Aliphatic acids; Betula pendula; Black liquor; Characterization; Lignin; Precipitation; Soda-AQ pulping
Contact information: Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland; *Corresponding author: hemanathan.k.kumar@jyu.fi
INTRODUCTION
Lignin is one of the most abundant natural polymers, and it is widely distributed throughout the plant kingdom (Sakakibara and Sano 2001). The main function of lignin is to give strength and mechanical support to the plant. In wood materials its content is normally 20% to 30% of the dry solids. The biosynthetic precursors of this amorphous, polyphenolic heteropolymer are comprised of three phenylpropanoid units (coniferyl, sinapyl, and p-coumaryl alcohols) that by various oxidative coupling reactions form a randomly cross-linked macromolecule with different inter-unitary linkages (Brunow et al. 1999). The structural building blocks are joined together by ether linkages and carbon-carbon bonds, and consistent with the close association between lignin and hemicelluloses in the wood cell wall, there are also chemical bonds between these constituents (Alén 2000a).
The effective removal of lignin from wood chips, called delignification, is performed to liberate wood fibers, which comprises the basis of chemical pulping (Sjöström 1993; Alén 2000b). Currently, about 90% of chemical pulp (about 130 million tons, annually) is produced by the dominant kraft (sulfate) process (Alén 2011). However, during kraft pulping, roughly half of the wood substance degrades (about 90% of lignin, 60% of hemicelluloses, and 10% of cellulose) and dissolves into the cooking liquor (black liquor (BL)). Due to this low selectivity of kraft pulping, BL contains, besides degraded lignin, a large amount of carbohydrate-derived material (mainly aliphatic carboxylic acids). BL is generally burned after evaporation in the recovery boiler to recover energy and cooking chemicals. Kraft lignin also can be partly separated from BL and used as a potential feedstock in the production of various chemicals and solid or liquid fuels.
In general, the recovery and versatile utilization of lignosulfonates from sulfite pulping is widely carried out (Fengel and Wegener 1989; Sjöström 1993; Mansouri and Salvadó 2006). However, despite the widespread availability, the chemical utilization of lignin fractions from kraft pulping is practiced only on a limited scale (Gilarranz et al. 1998; Lora and Glasser 2002; Calvo-Flores and Dobado 2010; Li and Ge 2011). This is mainly due to their heterogeneous nature, and the lack of capable economic methods in their isolation with high purity (Chakar and Ragauskas 2004; García et al. 2009). During kraft pulping, the lignin is degraded and its phenolic hydroxyl groups are dissociated to sodium phenolates (alkali lignin). The alkali lignin can be recovered through the precipitation of BL by decreasing the BL pH with an acidifying agent such as CO2 or H2SO4(Alén et al. 1979; Uloth and Wearing 1989; Nagy et al. 2010; Tomani 2010). However, by acidification with H2SO4, an effective way of handling the Na2SO4 byproduct is required (Alén 2011; Kumar and Alén 2014). The industrial applications of alkali lignins from different origins primarily depends on the economic factor and a better understanding of their specific properties, structures, and recovery methods.
In a previous study, an electrochemical process concept to recover NaOH from Na2SO4 formed during the acidification of BL with H2SO4 was outlined (Kumar and Alén 2014). In combination with the recovery of the aliphatic carboxylic acids from BL, the main aim of this study was to characterize the precipitated sulfur-free lignin fractions obtained from the hardwood soda-anthraquinone (soda-AQ) BL by carbonation or by acidification with H2SO4 after carbonation or directly.The utilization possibilities of the separated lignin feedstocks will be clarified in forthcoming investigations.
EXPERIMENTAL
Black Liquor and Lignin Samples
The BL sample was obtained from a conventional laboratory-scale soda-AQ cook of industrial silver birch (Betula pendula) chips. The cook was conducted with an 18 L rotating stainless steel digester. The chips employed for pulping were screened according to standard SCAN-CM 40:01 (2001), and the chip thickness fraction between 7 mm and 13 mm was accepted. Chips with knots and bark residues were also eliminated. The cooking conditions selected were based on the previous study (Kumar and Alén 2014). The BL was separated from the pulp/liquor mixture by pressing it into a nylon-woven fabric bag and stored at about 4 °C prior to further experiments.
The “carbonated lignin” (Fig. 1a) was prepared by treating the initial BL (pH of about 13.5) (0.6 L) with CO2 to a pH of approximately 8.5 in a pressurized stainless steel reactor (0.8 L) at 80 °C and approximately 1.5 bar for 40 min (Alén et al. 1979). The precipitated lignin was separated from the liquid phase (“carbonated BL”) by centrifugation (3000 rpm for 30 min) and freeze-dried (-50 °C at about 0.001 mbar) for 24 h (Kumar and Alén 2014). Finally, the carbonated lignin was crushed and stored at -18 °C prior to further experiments. The carbonated BL was then acidified with 2 M H2SO4 to a pH of about 2 at room temperature (Fig. 1a). The precipitated lignin (“acidified lignin”) was centrifuged, vacuum dried, and stored as the carbonated lignin. Additionally, the initial BL was also directly acidified with 2 M H2SO4 to a pH of about 2 (Fig. 1b). The precipitated lignin (“directly acidified lignin”) was handled and stored as the other lignin samples. All the chemicals and solvents used were of analytical grade.
Fig. 1. Schematic representations of the separation methods for producing crude fractions of lignin and aliphatic carboxylic acids from black liquor by carbonation followed by acidification with H2SO4 (a) or directly by acidification with H2SO4 (b)
Analysis of Lignin
Fourier transform infrared (FTIR) spectra were recorded with a Tensor27 FT-IR spectrometer (Bruker GmbH, Karlsruhe, Germany). The spectra were taken as an average of 32 scans between 400 cm-1 and 4000 cm-1, with a resolution of 4 cm-1. The results were stored and analyzed with the Bruker OPUS version 6.5 software.
Ultraviolet (UV) spectra were measured with a Beckman DU 640 spectrometer (Beckman Instruments, Inc., Fullerton, CA, USA) between 205 nm and 300 nm. Prior to the analyses, the samples were dissolved into 0.1 M NaOH solution at a concentration of 30 µg/mL.
The content of sulfur in lignin samples was determined using an energy dispersive X-ray fluorescence (ED XRF) spectrometer (Bruker, GmbH, Germany). The method was first calibrated with thermomechanical pulps with a wide range of sulfur concentration (40 to 5900 mg sulfur/kg pulp).
The molecular weight distributions (MWDs) were determined by gel permeation chromatography (GPC) using a Waters HPLC system (Waters Corporation, Milford, MA, USA). Before the measurements, the lignin samples (about 3 mg/mL) were dissolved into the eluent (0.1 M NaOH) and filtered with a nylon syringe filter (0.45 µm). A column (460 mm × 10 mm i.d.) filled with a Superdex 75 gel (GE Healthcare Bio-Sciences AB, Uppsala, Sweden) was used for the separation of lignin fragments. The flow-rate of the eluent was 0.3 mL/min at room temperature. Detection was carried out using a Waters 996 photodiode array (PDA) detector within a wavelength range of 240 nm to 400 nm, and 280 nm was used for the determination of molecular weights. Calibration of the GPC system was carried out with a commercial set of protein standards (Sigma-Aldrich, St. Louis, MO, USA) (molar mass (MM) range was between 6,500 g/mol and 2,000,000 g/mol) and a number of lignin-like monomer/oligomer model compounds (vanillin, dehydrodiaceto-vanillone, rutin, and tannic acid; MM range was between 152 g/mol and 1,701 g/mol (Lehto et al. 2015).
Qualitative 13C nuclear magnetic resonance (NMR) was performed with Bruker 300 and 400 spectrometers with DMSO-d6 as the solvent at a sample concentration of 167 mg/mL using a 30° pulse angle with a recycle delay time of 2 s. An acquisition time of 1.82 s and an observed pulse of 6.5 μs were used for a 75 MHz spectrometer (acidified lignin) and 1.48 s and 6.0 μs for a 101 MHz spectrometer (carbonated lignin). The spectra were analyzed with Topspin software (Bruker Corporation, Billerica, MA, USA), and the peaks were assigned the chemical shift with respect to 39.51 (for (CD3)2SO). The analyses included a decoupling mode to reduce the Nuclear Overhauser Enhancement (NOE) (Gottlieb et al. 1997).
Determination of Aliphatic Carboxylic Acids
Volatile acids (formic and acetic acids) were determined as their benzyl esters with a gas chromatograph equipped with a flame-ionization detector (GC/FID) using an Agilent 7820A Series instrument (Agilent Technologies, Santa Clara, CA, USA) (Alén et al. 1985) A capillary column Agilent HP-5 (30 m x 0.32 mm I.D., and a film thickness 0.25 µm) was used. The column oven temperature program was 3 min at 60 °C, 3 °C/min to 150 °C, 15 °C/min to 230 °C, and 5 min at 230 °C. The injection port had a temperature of 280 °C, and the FID temperature was 280 °C. Before the GC analysis, the acids were first liberated from their sodium salts with a strongly acidic cation exchange resin (Amberlyst 15), converted into their tetra-n-butylammonium (TBA) salts with tetra-n-butylammonium hydroxide (TBAH), and then converted into their benzyl esters with a reagent containing benzyl bromide in acetone. An aqueous solution of crotonic acid was used as an internal standard (IS).
Hydroxy carboxylic acids were determined by GC/FID (Alén et al. 1984). A capillary column Agilent HP-5 (30 m x 0.32 mm I.D., and a film thickness 0.25 µm) were used. The column oven temperature program was 5 min at 60 °C, 2 °C/min to 200 °C, 30 °C/min to 290 °C, and 15 min at 290 °C. The injection port had a temperature of 290 °C, and the FID temperature was 300 °C. In this quantitative determination, the sodium salts of the acids were first converted into their respective ammonium salts with a cation exchange resin (Amberlite IRC-50) and then per(trimethylsilyl)ated with a mixture of 99% N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and 1% trimethylchlorosilane (TMCS) in pyridine before the GC analysis. An aqueous solution of xylitol was used as an internal standard. The identification of the chromatographic peaks was conducted by a gas chromatograph equipped with a mass selective detector (GC/MSD) with a capillary column Agilent HP-5 (30 m x 0.25 mm I.D., and a film thickness 0.25 µm) under the same conditions used in GC/FID. The results were analyzed with the Enhanced ChemStation G1701CA software (version C.00.00, Agilent Technologies), and the mass spectra were compared to those in the Wiley 7th Ed. library software (McLafferty 2005).
RESULTS AND DISCUSSION
No important differences were detected in the relative proportions of aliphatic carboxylic acids in the BL residues obtained after carbonation and/or acidification with H2SO4 (Table 1). This finding suggested that no specific adsorption of individual aliphatic acids on the lignin precipitates took place. The differences in the total concentrations of aliphatic carboxylic acids in the BL residues were mainly due to an increase in the liquor volume (1:1.3) when added to the aqueous H2SO4 solution.
The initial concentration of sodium in BL was around 26.5 g/L. Almost half of the initial lignin was precipitated during carbonation (to a pH of about 8.5) with the simultaneous formation of NaHCO3/Na2CO3. Neutralization of the phenolic hydroxyl groups occurs in the pH range of 9 to 11, and a further lowering of the pH to about 2 liberates the carboxylic groups (pKa 3 to 5) with an enhanced precipitation of lignin (Alén 2011). For this reason, about 90% of the initial lignin was expected to be precipitated by acidification (pH of about 2) of the carbonated BL or by direct acidification of the initial BL with dilute sulfuric acid (Alén et al. 1979). These acidifications resulted in the formation of Na2SO4.
Table 1. Relative Composition of Aliphatic Carboxylic Acids in Birch Soda-AQ Black Liquors after Carbonation, Carbonation and Acidification, and Direct Acidification (% of the Total Acids)*
*Total amounts of acids in the carbonated, carbonated and acidified, and directly acidified black liquors were 42.4 g/L, 31.6 g/L, and 27.3 g/L, respectively.
**α- and β-isomers (i.e., erythro– and threo-isomers, respectively).
The FTIR spectra of the precipitated lignins under different conditions are shown in Fig. 2. The spectra almost followed the similar band patterns, except at 430 cm-1 to 600 cm-1, which was assumed to be C-S stretching and only observed in the spectrum of sulfuric acid precipitated lignins (Ibrahim et al. 2004). Table 2 lists the characteristic band assignments for the FTIR spectra of the three different lignin samples.
Fig. 2. IR spectra of lignins precipitated from birch soda-AQ black liquor
Table 2. Characteristic Band Assignments for the Precipitated Birch Soda-AQ Lignins by Acidification
* Only for lignin samples precipitated with H2SO4.
Note: Band interpretations were based on Faix (1992), Sun and Tomkinson (2001), Ibrahim et al.(2004), Tejado et al. (2007), and Lisperguer et al. (2009).
The UV absorption spectra for the three lignin samples are shown in Fig. 3. Because of its aromatic nature, lignin has a strong absorption potential for UV light and exhibits characteristic maxima in the UV light region (Alén and Hartus 1988; Lin 1992). All spectra showed a maximum absorbance at 220 nm, and it increased in the following order: carbonated lignin > directly acidified lignin > acidified lignin. Differences in the absorbance values (i.e., in the absorptivity values) were probably due to inorganic salt impurities (Ibrahim et al. 2004).
The elemental analysis of lignin in ED XRF (Fig. 4) showed that the sulfur content in acidified lignin and directly acidified lignin was about 15 mg/g and 16 mg/g, respectively. On the other hand, only negligible amount (< 1 ppm) of sulfur was present in the carbonated lignin.
Fig. 3. UV spectra of lignins precipitated from birch soda-AQ black liquor
Fig. 4. ED XRF spectra of lignins precipitated from birch soda-AQ black liquor
The normalized MWDs of the precipitated lignins are shown in Fig. 5. Table 3 gives the weight average (Mw) and number average (Mn) molecular weights and polydispersity (Mw/Mn) of these lignin fractions. The results indicated that the Mw and Mw/Mn of the carbonated lignin was somewhat higher than those of the acidified lignins. This trend was expected since the low-molecular-weight lignin fractions precipitated at lower pH values are generally more water soluble than those with higher molecular masses (Pakkanen and Alén 2012).
Fig. 5. Normalized MWDs of lignins precipitated from birch soda-AQ black liquor
Table 3. Weight Average (Mw) and Number Average (Mn), and Polydispersity (Mw/Mn) of Lignins Precipitated from Birch Soda-AQ Black Liquor
Fig. 6. 13C NMR spectra of lignins precipitated from birch soda-AQ black liquor
Due to the close structural similarities of the precipitated lignins, their 13C NMR spectra were also almost identical (Fig. 6). In these spectra, the weak peaks in the chemical shift ranged from 130 ppm to 170 ppm, corresponding to the aromatic carbons attached to oxygen atoms (=C-O-), strong peaks from 100 ppm to 130 ppm to the secondary aromatic carbons (=CH-C), weak peaks from 100 ppm to 130 ppm to the tertiary aromatic carbons (=C-C), strong peaks in the range 50 ppm to 80 ppm to the (OCH3) carbons, and other aliphatic carbons attached to oxygen atoms, and the peaks in the range 0 ppm to 40 ppm to the aliphatic carbons (Stoklosa et al. 2013).
CONCLUSIONS
- Today, there is an increased interest to gradually replace fossil carbon sources by alternative raw materials. With this respect, practically sulfur-free lignin from pulping seems to be one of the attractive feedstock possibilities. In this study, to promote the utilization of hardwood alkali lignins, three fractions of lignin from birch soda-AQ pulping were characterized. The fractions originated from carbonation (pH to about 8.5) or acidification (pH to about 2) with H2SO4 after carbonation or directly.
- All of the experimental data (FTIR, UV, and 13C NMR spectra, as well as molecular weight distributions) indicate only small differences between the precipitated lignins and thus, their equal chemical utilization seems possible.
- However, the carbonated lignin fraction contained slightly more chemically bound sodium than the acidified lignin fractions, since the pKa values of the phenolic hydroxyl and carboxylic acid groups are 9 to 11 and 3 to 5, respectively.
- In addition, the results indicated that no selective absorption of aliphatic carboxylic acids, the second main constituents of black liquor, takes place on lignin precipitates.
ACKNOWLEDGMENTS
The authors gratefully acknowledge the financial support of the Foundation for Research of Natural Resources in Finland (Suomen Luonnonvarain Tutkimussäätiö).
REFERENCES CITED
Alén, R. (2000a). “Structure and chemical composition of wood,” in: Forest Products Chemistry, P. Stenius (ed.), Fapet Oy, Helsinki, Finland, pp. 11-57.
Alén, R. (2000b). “Basic chemistry of wood delignification,” in: Forest Products Chemistry, P. Stenius (ed.), Fapet Oy, Helsinki, Finland, pp. 58-104.
Alén, R. (2011). “Principles of biorefining,” in: Biorefining of Forest Resources, R. Alén (ed.), Paper Engineers’ Association, Helsinki, Finland, pp. 55-114.
Alén, R., and Hartus, T. (1988). “UV spectrophotometric determination of lignin from alkaline pulping liquors,” Cell. Chem. Technol. 22(6), 613-618.
Alén, R., Jännäri, P., and Sjöström, E. (1985). “Gas-liquid chromatographic determination of volatile fatty acids C1-C6, and lactic acid as their benzyl esters on a fused-silica capillary column,” Finn. Chem. Lett. 12(5), 190-192.
Alén, R., Niemelä, K., and Sjöström, E. (1984). “Gas-liquid chromatographic separation of hydroxy monocarboxylic acids and dicarboxylic acids on a fused-silica capillary column,” J. Chromatogr. A. 301, 273-276.
Alén, R., Patja, P., and Sjöström, E. (1979). “Carbon dioxide precipitation of lignin from pine kraft black liquor,” TAPPI 62(11), 108-110.
Brunow, G., Lundquist, K., and Gellerstedt, G. (1999). “Lignin,” in: Analytical Methods in Wood Chemistry, Pulping, and Papermaking, E. Sjöström, and R. Alén (eds.), Springer Verlag, Heidelberg, Germany, pp. 77-124.
Calvo-Flores, F. G., and Dobado, J. A. (2010). “Lignin as renewable raw material,” ChemSusChem. 3(11), 1227-1235. DOI: 10.1002/cssc.201000157
Chakar, F. S., and Ragauskas, A. J. (2004). “Review of current and future softwood kraft lignin process chemistry,” Ind. Crop. Prod. 20(2), 131-141. DOI: 10.1016/j.indcrop.2004.04.016
Faix, O. (1992). “Fourier transform infrared spectroscopy,” in: Methods in Lignin Chemistry, S. Y. Lin, and C. W. Dence (eds.), Springer Verlag, Heidelberg, Germany, pp. 83-109.
Fengel, D., and Wegener, G. (1989). Wood – Chemistry, Ultrastructure, Reactions, Walter de Gruyter, Berlin, Germany.
García, A., Toledano, A., Serrano, L., Egüés, I., González, M., Marín, F., and Labidi, J. (2009). “Characterization of lignins obtained by selective precipitation,” Sep. Purific. Technol. 68(2),193-198. DOI: 10.1016/j.seppur.2009.05.001
Gilarranz, M., Rodriguez, F., Oliet, M., and Revenga, J. (1998). “Acid precipitation and purification of wheat straw lignin,” Separ. Sci. Technol. 33(9), 1359-1377. DOI:10.1080/01496399808544988
Gottlieb, H. E., Kotlyar, V., and Nudelman, A. (1997). “NMR chemical shifts of common laboratory solvents as trace impurities,” J. Org. Chem. 62, 7512-7515. DOI: 10.1021/jo971176v
Ibrahim, M. M., Chuah, S., and Rosli, W. W. (2004). “Characterization of lignin precipitated from the soda black liquor of oil palm empty fruit bunch fibers by various mineral acids,” AJSTD. 21(1), 57-68.
Kumar, H., and Alén, R. (2014). “Partial recovery of aliphatic carboxylic acids and sodium hydroxide from hardwood black liquor by electrodialysis,” Ind. Eng. Chem. Res. 53(22), 9464-9470. DOI: 10.1021/ie5006004
Lehto, J., Pakkanen, H., and Alén, R. (2015) “Characterization of lignin dissolved during alkaline pretreatment of softwood and hardwood,” J. Wood Chem. Technol. 35(5), 337-347. DOI: 10.1080/02773813.2014.965332
Li, Z., and Ge, Y. (2011). “Extraction of lignin from sugar cane bagasse and its modification into a high performance dispersant for pesticide formulations,” J. Braz. Chem. Soc. 22(10), 1866-1871. DOI: 10.1590/S0103-50532011001000006
Lin, S. Y. (1992). “Ultraviolet spectrophotometry,” in: Methods in Lignin Chemistry, S. Y. Lin, and C. W. Dence (eds.), Springer Verlag, Heidelberg, Germany, pp. 217-232.
Lisperguer, J., Perez, P., and Urizar, S. (2009). “Structure and thermal properties of lignins: Characterization by infrared spectroscopy and differential scanning calorimetry,” J. Chil. Chem. Soc. 54(4), 460-463. DOI: 10.4067/S0717-97072009000400030
Lora, J. H., and Glasser, W. G. (2002). “Recent industrial applications of lignin: a sustainable alternative to nonrenewable materials,” J. Polym. Environ. 10(1), 39-48. DOI: 10.1023/A:1021070006895
Mansouri, N. E. E., and Salvadó, J. (2006). “Structural characterization of technical lignins for the production of adhesives: Application to lignosulfonate, kraft, soda-anthraquinone, organosolv and ethanol process lignins,” Ind. Crop. Prod. 24(1), 8-16. DOI: 10.1016/j.indcrop.2005.10.002
McLafferty, F. W. (2005). Wiley Registry of Mass Spectra Data (7th ed.). Wiley-Blackwell, New York, NY, USA.
Nagy, M., Kosa, M., Theliander, H., and Ragauskas, A. J. (2010). “Characterization of CO2precipitated Kraft lignin to promote its utilization,” Green Chem.12, 31-34. DOI: 10.1039/B913602A
Pakkanen, H., and Alén, R. (2012). “Molecular mass distribution of lignin from the alkaline pulping of hardwood, softwood, and wheat straw,” J. Wood Chem. Technol. 32(4), 279-293. DOI: 10.1080/02773813.2012.659321
Sakakibara, A., and Sano, Y. (2001). “Chemistry of lignin,” in: Wood and Cellulosic Chemistry, D. N.-S. Hon, and N. Shiraishi (eds.), Marcel Dekker Inc., New York, NY, USA, pp. 109-173.
SCAN-CM 40:01 (2001). “Wood chips for pulp production,” Scandinavian Pulp, Paper and Board Testing Committee, Stockholm, Sweden.
Sjöström, E. (1993). Wood Chemistry – Fundamentals and Applications (2nd Ed.), Academic Press, San Diego, CA, USA.
Stoklosa, R. J., Velez, J., Kelkar, S., Saffron, C. M., Thies, M. C., and Hodge, D. B. (2013). “Correlating lignin structural features to phase partitioning behavior in a novel aqueous fractionation of softwood kraft black liquor,” Green Chem. 15, 2904-2912. DOI: 10.1039/C3GC41182F
Sun, R., and Tomkinson, J. (2001). “Fractional separation and physico-chemical analysis of lignins from the black liquor of oil palm trunk fibre pulping,” Sep. Purific. Technol. 24(3), 529-539. DOI: 10.1016/S1383-5866(01)00153-8
Tejado, A., Peña, C., Labidi, J., Echeverria, J. M., and Mondragon, I. (2007). “Physico-chemical characterization of lignins from different sources for use in phenol-formaldehyde resin synthesis,” Bioresour. Technol. 98(8), 1655-1663. DOI:10.1016/j.biortech.2006.05.042
Tomani, P. (2010) “The lignoboost process,” Cell. Chem. Technol. 44(1), 53-58.
Uloth, V. C., and Wearing, J. T. (1989) “Kraft lignin recovery: Acid precipitation versus ultrafiltration. Part I,” Pulp Pap. Canada. 90(9), 67-71.
Article submitted: July 2, 2016; Peer review completed: August 21, 2016; Revised version received and accepted: September 22, 2016; Published: October 3, 2016.
DOI: 10.15376/biores.11.4.9869-9879