Relationship between lignin structure and delignification degree in Pinus pinaster kraft pulps

This study examines the structure of residual and dissolved lignins from Pinus pinaster pulps obtained at different degrees of delignification by laboratory conventional kraft pulping. The cooking H factor was varied from 85 to 8049. The residual and dissolved lignin samples were characterised by elemental analysis, residual carbohydrate content, permanganate oxidation and 13C NMR spectroscopy. The reflectance factor of the pulps was also determined in order to tentatively correlate the delignification degree and residual lignin structure with the pulp colour. The obtained results confirmed that the delignification degree increases the condensation of the lignin structure, which might have an influence upon the observed increased pulp colour. The lack of selectivity of kraft pulping process in the case of more delignified pulps was also shown.     

Delignification kinetics of corn stover in lime pretreatment

Corn stover was pretreated with excess calcium hydroxide (0.5 g Ca(OH)(2)/g raw biomass) in non-oxidative and oxidative conditions at 25, 35, 45, and 55 degrees C. The delignification kinetic model of corn stover used three first-order reactions with following forms: W(L) = 0.09 x exp(-infinity x t) + 0.28 x exp(-k(2) x t) + 0.63 x exp(-k(3) x t) in non-oxidative pretreatment; W(L) = 0.16 x exp(-infinity x t) + 0.27 x exp(-k(2) x t) + 0.57 x exp(-k(3) x t) in oxidative pretreatment. The first term corresponds to the initial phase, which is essentially infinite at the time scale of the reaction (weeks). The second and third terms correspond to the bulk and residual phases of delignification. The activation energies for delignification in the oxidative lime pretreatment reactions were estimated as 50.15 and 54.21 kJ/mol in the bulk and residual phases, respectively, which are similar to the Kraft delignification of bagasse, but much less than in Kraft delignification of wood.     

Catalytic solvent delignification of agricultural residues: Organic catalysts

The effects of moderate-temperature aqueous butanol pretreatment of rice straw on several organic catalysts have been studied. Maximum delignification was obtained with an aromatic organic acid catalyst. Presoaking of straw in aqueous improved delignification, particularly in high solid-liquid rations. However, due to the difficulty of penetration of lignin into the solvent phase, an increase in the solid-liquid ratio appears to affect delignification. A two-stage catalytic solvent process involving presoaking at 80 degrees C followed by delignification at 120 degrees C resulted in 83% removal of lignin in aqueous-butanol, whereas 75% lignin removal was possible in ethanol. Higher reduction in the crystallinity was possible with etanol. Lignin produced by the solvent process offers desirable physical properties for polymer applications compared to Kraft lignin.     

Influence of dimethyl formamide pulping of wheat straw on cellulose degradation and comparison with Kraft process

The pulping of wheat straw with dimethyl formamide was studied in order to investigate the effects of the cooking variables (temperature (190 degrees C, 200 degrees C, and 210 degrees C) and time (120 min, 150 min, and 180 min) and organic solvent ratio (30%, 50%, and 70%) dimethyl formamide (DMF+water) value) on the degradation of cellulose and degree of polymerization (DP) of organosolv pulp. The SCAN viscosity was applied to estimating the extent of cellulose degradation produced by cooking condition and then, it was compared with Kraft pulp at equal Kappa number. Response of pulp and handsheets properties to the process variables were analyzed using statistical software (MINITAB 14). The process variables (cooking temperature and cooking time) must be set at low variables with high DMF ratio in order to ensure a high yield and high SCAN viscosity. Also, pulps with high mechanical properties can be acceptably obtained at 210 degrees C for 150 min with 50% DMF. Generally, the cooking temperature was a significant factor while the cooking time and DMF ratio had a smaller role. By the comparison of Kraft and organosolv pulp, it can be resulted that DMF basically had improvement role on reducing of cellulose degradation by reason of high SCAN viscosity of organosolv pulp than Kraft pulp under equal kappa number and, scanning electron microscopy (SEM) of obtained pulp. Consequently, the protective action of organic solvent on non-cellulosic polysaccharides of wheat straw against degradation under Kraft pulping conditions was pointed as a main reason of the fairly high yield of organosolv pulps.     

A new pulping process for wheat straw to reduce problems with the discharge of black liquor

Aqueous ammonia mixed with caustic potash as wheat straw pulping liquor was investigated. The caustic potash did not only reduce the NH3 usage and cooking time, but also provided a potassium source as a fertilizer in the black liquor. Excess NH3 in the black liquor was recovered and reused by batch distillation with a 98% recovery rate of free NH3. The black liquor was further treated for reuse by coagulation under alkaline conditions. The effects of different flocculation conditions, such as the dosage of 10% aluminium polychloride, the dosage of 0.1% polyacrylamide, the reaction temperature and the pH of the black liquor on the flocculating process were studied. The supernatant was recycled as cooking liquor by adding extra NH4OH and KOH. The amount of delignification and the pulp yield for the process remained steady at 82-85% and 48-50%, respectively, when reusing the supernatant four times. The coagulated residues could be further processed as solid fertilizers. This study provided a new pulping process for wheat straw to reduce problems of discharge black liquor.     

Pretreatment of eucalyptus wood chips for enzymatic saccharification using combined sulfuric acid-free ethanol cooking and ball milling

A combined sulfuric acid-free ethanol cooking and pulverization process was developed in order to achieve the complete saccharification of the cellulosic component of woody biomass, thereby avoiding the problems associated with the use of strong acid catalysts. Eucalyptus wood chips were used as a raw material and exposed to an ethanol/water/acetic acid mixed solvent in an autoclave. This process can cause the fibrillation of wood chips. During the process, the production of furfural due to an excessive degradation of polysaccharide components was extremely low and delignification was insignificant. Therefore, the cooking process is regarded not as a delignification but as an activation of the original wood. Subsequently, the activated solid products were pulverized by ball-milling in order to improve their enzymatic digestibility. Enzymatic hydrolysis experiments demonstrated that the conversion of the cellulosic components into glucose attained 100% under optimal conditions. Wide-angle X-ray diffractometry and particle size distribution analysis revealed that the scale affecting the improvement of enzymatic digestibility ranged from 10 nm to 1 microm. Field emission scanning electron microscopy depicted that the sulfuric acid-free ethanol cooking induced a pore formation by the removal of part of the lignin and hemicellulose fractions in the size range from a few of tens nanometers to several hundred nanometers.     

Effect of structural features on enzyme digestibility of corn stover

Corn stover was pretreated with excess calcium hydroxide (0.5 g Ca(OH)2/g raw biomass) in non-oxidative and oxidative conditions at 25, 35, 45, and 55 degrees C. The enzymatic digestibility of lime-treated corn stover was affected by the change of structural features (acetylation, lignification, and crystallization) resulting from the treatment. Extensive delignification required oxidative treatment and additional consumption of lime (up to 0.17 g Ca(OH)2/g biomass). Deacetylation reached a plateau within 1 week and there were no significant differences between non-oxidative and oxidative conditions at 55 degrees C; both conditions removed approximately 90% of the acetyl groups in 1 week at all temperatures studied. Delignification highly depended on temperature and the presence of oxygen. Lignin and hemicellulose were selectively removed (or solubilized), but cellulose was not affected by lime pretreatment in mild temperatures (25-55 degrees C), even though corn stover was contacted with alkali for a long time, 16 weeks. The degree of crystallinity slightly increased from 43% to 60% with delignification because amorphous components (lignin, hemicellulose) were removed. However, the increased crystallinity did not negatively affect the 3-d sugar yield of enzymatic hydrolysis. Oxidative lime pretreatment lowered the acetyl and lignin contents to obtain high digestibility, regardless of crystallinity. The non-linear models for 3-d hydrolysis yields of glucan (Y(g)), xylan (Y(x)), and holocellulose (Y(gx)) were empirically established as a function of the residual lignin (L) for the corn stover pretreated with lime and air.     

Influence of rice straw cooking conditions in the soda-ethanol-water pulping on the mechanical properties of produced paper sheets

A normalized design was used to examine the influence of independent variables (alcohol concentration, cooking time and temperature) in the catalytic soda-ethanol pulping of rice straw on various mechanical properties (breaking length, burst, tear index and folding endurance) of paper sheets obtained from each pulping process. An equation of each dependent variable as a function of cooking variables (independent variables) was obtained by multiple non-linear regression using the least square method by MATLAB software for developing of empirical models. The ranges of alcohol concentration, cooking time and temperature were 40-65% (w/w), 150-180 min and 195-210 degrees C, respectively. Three-dimensional graphs of dependent variables were also plotted versus independent variables. The optimum values of breaking length, burst and tear index and folding endurance were 4683.7 (m), 30.99 (kN/g), 376.93 (mN m2/g) and 27.31, respectively. However, short cooking time (150 min), high ethanol concentration (65%) and high temperature (210 degrees C) could be used to produce papers with suitable burst and tear index. However, for papers with best breaking length and folding endurance low temperature (195 degrees C) was desirable. Differences between optimum values of dependent variables obtained by normalized design and experimental data were less than 20%.     

Kinetics of polysaccharide degradation during ethanol–alkali delignification of giant reed—Part 1. Cellulose and xylan

The degradation kinetics of the principal polysaccharides (cellulose and xylan) of the agro-fibre crop Arundo donax L. (giant reed) during ethanol–alkali delignification is reported. Based on the properties of a multi-component reaction system, the degradation kinetics of both polysaccharides was accurately described in terms of two simultaneous irreversible first-order reactions corresponding to removal of two kinetically homogeneous fractions. The moderate cellulose losses during pulping (about 4.5%) result mainly from the removal of the more reactive cellulose fraction, that accounted for 4% of initial cellulose. The bulk of the cellulose (96%) degrades slowly with three orders lower rate with pulping progress. The apparent activation energy of cellulose fractions degradation was estimated as 105.2 and 106.5 kJ mol⁻¹, respectively. Substantial loss of xylan during pulping (about 55%, as a homoxylan) is caused by fast removal of the first very reactive fraction, covering about 48% of total xylan. The degradation rate of the second xylan fraction is only one order higher of the bulk cellulose degradation. The activation energy of xylan fractions degradation was found as 74.4 and 140.9 kJ mol⁻¹, respectively.     

Influence of dimethyl formamide pulping of bagasse on pulp properties

Organosolv pulping of bagasse was conducted following a central composite design using a two-level factorial plan involving three pulping variables (temperature: 190-210 degrees C, time: 120-180 min, organic solvent charge: 40-60% dimethyl formamide). Responses of pulp properties (yield and holocellulose, alpha-cellulose, kappa number, ash and ethanol-dichloromethane extractives contents) and the pH of the resulting wastewater to the process variables were analyzed using statistical software (MINITAB). Main factor analysis revealed that optimum pulp has the following characteristics: 82.7% (yield), 92.9 (kappa number), 95.84% (holocellulose), 83.53% (alpha-cellulose), 1.403% (ash), 2.562% (ethanol-dichloromethane extractives contents) and 6.39 (pH). These results showed that acceptable properties of pulps could be gained at 200-210 degrees C for 150 min and 40-60% DMF. Based on these results, this method could be used for pulping of bagasse equivalent NSSC concerning high yield at a fixed kappa number. In addition, bagasse could be pulped with ease to approximately 55% yield with a kappa number approximately 31. Numerical analyses showed that cooking temperature had the greatest influence on properties of obtained pulps within the DMF concentrations and cooking time as cooking variables.     

A model co-ordinating the elongation of all leaves of a sorghum cultivar was applied to both Mediterranean and Sahelian conditions

Sorghum leaf development was analysed at plant level by analysing the time-course of elongation and identifying the beginning and end of the elongation phases of each leaf blade. This was done with destructive and non-destructive measurements in 14 experiments carried out during several growing periods in Southern France and Sahelian Africa. Elongation of each blade was characterized by the succession of a nearly exponential phase and a linear phase. For a given blade and provided that time was expressed in thermal units, initiation, beginning and end of the linear phase, and time-courses of elongation rate were strikingly similar in all experiments, except in environments with a maximum air temperature close to 40 degrees C and a maximum vapour pressure deficit close to 6 kPa. The relative elongation rate during the exponential phase declined with leaf number from 0.08 to 0.02 degrees Cd(-1), while the duration of this phase increased from 140 to 320 degrees Cd. By contrast, the absolute elongation rate during the linear phase was nearly constant from leaf 8 onwards. This phase was shorter than the exponential phase regardless of leaf position, but accounted for the largest part of blade length. A strict pattern of leaf development was observed at the whole plant level, whereby dates of elongation events and leaf and ligule appearance, represented on a thermal time scale, were linearly related to phytomer number. This pattern exhibited a simultaneous elongation cessation of the last-formed leaves and a mismatch between real and apparent (from leaf to ligule appearance) elongation duration.     

Alkaline pulping of some eucalypts from Sudan

Four eucalypts (Eucalyptus camaldulensis, Eucalyptus microtheca, Eucalyptus tereticornis and Eucalyptus citriodora) grown in Sudan were examined for their suitability for pulping and papermaking with different alkaline methods. Their physical, morphological and chemical characteristics are reported. The pulping trials with E. citriodora and E. tereticornis were carried out using the kraft-AQ, soda-AQ, modified AS/AQ (ASA), ASAM and kraft methods. For the other two species, only the ASAM and the kraft process were applied. ASAM pulping gave the best results in terms of yield, degree of delignification, mechanical and optical pulp properties. The best pulps, obtained in kraft and ASAM cooking of E. citriodora, were bleached to 88% ISO brightness in a totally chlorine free bleaching sequence (OQ1O/PQ2P). The bleached pulps, especially the ASAM pulp, showed good papermaking properties and would be suitable for manufacture of writing and printing grades of paper.     

Production and characterization of a thermostable alpha-amylase from Nocardiopsis sp. endophyte of yam bean

Thermostable amylolytic enzymes have been currently investigated to improve industrial processes of starch degradation. Studies on production of alpha-amylase by Nocardiopsis sp., an endophytic actinomycete isolated from yam bean (Pachyrhizus erosus L. Urban), showed that higher enzyme levels were obtained at the end of the logarithmic growth phase after incubation for 72 h at pH 8.6. Maximum activity of alpha-amylase was obtained at pH 5.0 and 70 degrees C. The isolated enzyme exhibited thermostable properties as indicated by retention of 100% of residual activity at 70 degrees C, and 50% of residual activity at 90 degrees C for 10 min. Extracellular enzyme from Nocardiopsis sp. was purified by fractional precipitation with ammonium sulphate. After 60% saturation produced 1130 U mg-1 protein and yield was 28% with purification 2.7-fold. The enzyme produced by Nocardiopsis sp. has potential for industrial applications.     

Pulping cardoon (Cynara cardunculus) with peroxyformic acid (MILOX) in one single stage

In this work, depithed cardoon stalk (Cynara cardunculus) has been used with the objective of obtaining bleachable pulps. The material, once properly prepared, was subjected to one-step peroxyformic acid delignification. In order to study the process, a face-centred second order factorial design was developed which allowed the determination of the influences of four variables: concentrations of formic acid and hydrogen peroxide in the cooking liquor and the time and temperature of the treatment.

Empirical mathematical models have been obtained which predict the yield, kappa index, residual lignin content, and viscosity of the pulps. These models demonstrate that in general the delignification was extensive, producing pulps with kappa indexes less than 25 in the majority of cases, with good yields in the range of 45–60%. However, the pulps seem to have been degraded in the reaction media, as can be deduced from the low viscosity values found: 260–520 mL/g.     

New perspectives for Paulownia fortunei L. valorisation of the autohydrolysis and pulping processes

This paper will consider the influence of the temperature of autohydrolysis or hydrothermal process from Paulownia fortunei L. to obtain a valuable liquid phase and a suitable solid phase to produce pulp. The solid phase resulting of autohydrolysis was subjected to organosolv pulping process and formed paper sheets, analyzing the influence of operational variables (viz., ethanol concentration, temperature and pulping time) on the yield, viscosity, tensile index, burst index, tear index and brightness. Maximum glucose and xylose contents and minimum paper sheets characteristic loss have been obtained at 190 degrees C authohydrolysis temperature. Suitable characteristics of paper sheets and acceptable yield, viscosity and kappa number of pulp could be obtained by operating at 180 degrees C temperature, 30min pulping time and 20% ethanol concentration. Under those conditions sheets paper with 27.4% ISO brightness, 28.87Nm/g tensile index, 1.22kPam(2)/g burst index and 1.23kNm(2)/g tear index could be obtained.     

Characterisation of the heterogeneous alkaline pulping kinetics of hemp woody core

A model was developed, based on the power law of growth and Avrami's concepts in nuclei growth to describe the heterogeneous nature of alkaline pulping kinetics, taking into account the effects of effective alkali concentration and temperature. It was then applied against published data to estimate model parameters. The final form of the model applied to alkaline pulping of thin hemp woody core in flow-through reactors could be represented by a first order rate equation with a time-dependent rate constant: [-dY/dt = A.[OH-]b.exp (-E/RT)n.Y.t(n-1). The rate equations applied for delignification, cellulose and xylan losses. It was found that the heterogeneous kinetic models predicted well the delignification and xylan loss of hemp woody core, with R2 values of 0.96 and 0.97, respectively. The model was, however, less accurate in predicting cellulose loss. The values n, which could represent the acceleration/deceleration extent of growth of reacting volumes, were found to be less than unity. This demonstrated the heterogeneous characteristics of alkaline pulping for hemp woody core.     

Stable cubic phases in codispersions of glucocerebroside and palmitoyloleoylphosphatidylethanolamine

The effect of glucocerebroside (GlcCer) on the structure and thermotropic phase behavior of aqueous dispersions of palmitoyloleoylphosphatidylethanolamine (POPE) has been examined using simultaneous small-angle and wide-angle X-ray diffraction methods. Binary mixtures of GlcCer:POPE in molar ratios of 2:100, 5:100, 10:100, 20:100, 30:100, and 40:100 were examined in the temperature range 20-90 degrees C. Cubic phase has been observed in binary mixtures comprised of molar ratios greater than 5:100 in the temperature range of 60-90 degrees C upon heating at a rate of 2 degrees C/min. The cubic phase is relatively stable and coexists with inverted hexagonal or lamellar phases. It persists in the codispersions throughout subsequent cooling scans to 30 degrees C. The space group of the cubic phase is determined to be Pn3m or Pn3. The lattice constant of the Pn3m cubic phase was found to be almost constant when it coexists with lamellar liquid-crystal phase. Marked temperature-dependent changes were observed when cubic phase coexists with hexagonal phase or lamellar-gel phases. This is the first report of cubic phases formed by codispersions of glycosphingolipids and phospholipids. The mechanism of cubic phase formation and the interaction between GlcCer and POPE is discussed in terms of the putative biological functions of glycolipids.     

Effect of pulping variables with dimethyl formamide on the characteristics of bagasse-fiber

Organosolv pulping of bagasse was conducted following a central composite design using a two-level factorial plan involving three pulping variables (temperature: 190-210 degrees C, time: 120-180 min, organic solvent ratio: 40-60% dimethyl formamide). Responses of pulp and handsheets properties to the process variables were analyzed using statistical software (MINITAB 14). Using values of the independent variables the variation ranges considered provided the following optimum values of the dependent variables: 82.7% (yield), 92.9 (kappa number), 1.403% (ash), 370 ml (freeness), 6290 m (breaking length), 9.4 (folding endurance), 5.955 mN m2 g(-1) (Tear index) and 2.811 kN g(-1) (Burst index) for pulps and handsheets. Results showed that acceptable physical and mechanical properties of pulps and papers similar the pulp used for bleaching could be achieved at 210 degrees C for 150 min and 50% DMF. These are the most suitable conditions for obtaining paper sheets with a high breaking length, tear and burst indices. Also bagasse could be pulped with ease to about 55.72% yield with kappa number approximately 35. The cooking temperature was a significant factor while the DMF ratio and cooking time were not as important in term of the properties of the resultant pulps and papers.     

A universal kinetic model for characterisation of the effect of chip thickness on kraft pulping

A kinetic model was developed to characterise the heterogeneous nature of kraft delignification kinetics, taking into account the effect of chip thickness. The final form of the model applied to kraft delignification can be represented by a first-order rate equation with a rate constant inversely proportional to a power function of chip thickness. Published laboratory results from kraft pulping of various lignocellulosic materials were used to validate the model. The outcomes confirm the significant effect of chip thickness on the delignification rate. The resultant model was used to predict the effect of chip thickness on the kappa distribution of kraft pulps.     

Comparative evaluation of acid and alkaline sulfite pretreatments for enzymatic saccharification of bagasses from three different sugarcane hybrids

Sugarcane bagasses from three experimental sugarcane hybrids and a mill‐reference sample were used to compare the efficiency and mode of action of acid and alkaline sulfite pretreatment processes. Varied chemical loads and reaction temperatures were used to prepare samples with distinguished characteristics regarding xylan and lignin removals, as well as sulfonation levels of residual lignins. The pretreatment with low sulfite loads (5%) under acidic conditions (pH 2) provided maximum glucose yield of 70% during enzymatic hydrolysis with cellulases (10 FPU/g) and β‐glucosidases (20 UI/g bagasse). In this case, glucan enzymatic conversion from pretreated materials was mostly associated with extensive xylan removal (70–100%) and partial delignification occurred during the pretreatment. The use of low sulfite loads under acidic conditions required pretreatment temperatures of 160°C. In contrast, at a lower pretreatment temperature (120°C), alkaline sulfite process achieved similar glucan digestibility, but required a higher sulfite load (7.5%). Residual xylans from acid pretreated materials were almost completely hydrolysed by commercial enzymes, contrasting with relatively lower xylan to xylose conversions observed in alkaline pretreated samples. Efficient xylan removal during acid sulfite pretreatment and during enzymatic digestion can be useful to enhance glucan accessibility and digestibility by cellulases. Alkaline sulfite process also provided substrates with high glucan digestibility, mainly associated with delignification and sulfonation of residual lignins. The results demonstrate that temperature, pH, and sulfite can be combined for reducing lignocellulose recalcitrance and achieve similar glucan conversion rates in the alkaline and acid sulfite pretreated bagasses. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 34:944–951, 2018