Use of high-boiling point organic solvents for pulping oil palm empty fruit bunches

Oil palm empty fruit bunches were used as an alternative raw material to obtain cellulosic pulp. Pulping was done by using high-boiling point organic solvents of decreased polluting power relative to classical (Kraft, sulphite) solvents but affording operation at similar pressure levels. The holocellulose, alpha-cellulose and lignin contents of oil palm empty fruit bunches (viz. 66.97%, 47.91% and 24.45%, respectively) are similar to those of some woody raw materials such as pine and eucalyptus, and various non-wood materials including olive tree prunings, wheat straw and sunflower stalks. Pulping tests were conducted by using ethyleneglycol, diethyleneglycol, ethanolamine and diethanolamine under two different sets of operating conditions, namely: (a) a 70% solvent concentration, 170 degrees C and 90 min; and (b) 80% solvent, 180 degrees C and 150 min. The solid/liquid ratio was six in both cases. The amine solvents were found to provide pulp with better properties than did the glycol solvents. Ethanolamine pulp exhibited the best viscosity and drainage index (viz. 636 mL/g and 17 degrees SR, respectively), and paper made from it the best breaking length (1709 m), stretch (1.95%), burst index (0.98 kN/g) and tear index (0.33 mNm(2)/g). Operating costs can be reduced by using milder conditions, which provide similar results. In any case, the amines are to be preferred to the glycols as solvents for this purpose.     

Hydrothermal treatment and ethanol pulping of sunflower stalks

The influence of temperature in the hydrothermal treatment of sunflower stalks on the composition of the liquid fraction obtained was examined. The remaining solid fraction was subjected to ethanol pulping in order to obtain pulp that was used to produce paper sheets. The pulp was characterized in terms of yield, kappa index, viscosity, and cellulose, hemicellulose and lignin contents; and the paper sheets in terms of breaking length, stretch, burst index and tear index. Hydrothermal treatment of the raw material at 190 degrees C provided a liquid phase with maximal hemicellulose-derived oligomers and monosaccharide (glucose, xylose and arabinose) contents (26.9 and 4.2 g/L, respectively). Pulping the solid fraction obtained by hydrothermal treatment at 180 degrees C, with 70% ethanol at a liquid/solid ratio of 8:1 at 170 degrees C for 120 min provided pulp with properties on a par with those of soda pulp from the sunflower stalks, namely: 36.3% yield, 69.1% cellulose, 12.6% hemicellulose, 18.2% lignin and 551 ml/g viscosity. Also, paper sheets obtained from the ethanol pulp were similar in breaking length (3.8 km), stretch (1.23%), burst index (1.15 kN/g) and tear index (2.04 m Nm(2)/g) to those provided by soda pulp.     

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.     

Influence of the holm oak soda pulping conditions on the properties of the resulting paper sheets

This paper reports on the influence of independent variables in the pulping of holm oak wood [viz. temperature (135-195 degrees C), cooking time (30-90 min) and soda concentration (10-20%)] on the properties of the resulting paper sheets. By using a central composite factorial design and a fuzzy neural model, equations relating each dependent variable to the different independent variables were derived that reproduced the experimental results for the dependent variables with errors less than 14%. Using a soda concentration of 17.5% at 195 degrees C for 30 min, it is possible to reduce the working capital (cost of chemical) and the capital investment, because it is operated with smaller values of the soda concentration and cooking time that maximum considered (20% of soda concentration and 90 min). The pulp yield thus obtained differed by less than 31.3% from the highest possible value; also, the resulting pulp and paper sheets had acceptable properties that differed by less than 21.10% from their optimum values.     

Pulping of holm oak wood. Influence of the operating conditions

This paper reports on the influence of independent variables in the pulping of holm oak wood (Quercus ilex L.) [viz. temperature (135-195 degrees C), cooking time (30-90min) and soda concentration (10-20%)] on the yield, holocellulose content, alpha-cellulose content, brightness and viscosity of the resulting pulp. By using a central composite factorial design, equations relating each dependent variable to the different independent variables were derived that reproduced the experimental results for the dependent variables with errors less than 5-15% in all cases. The highest pulp yield (56.9%) was obtained with the lowest values of the operating variables. However, obtaining the optimum holocellulose content, alpha-cellulose content and viscosity (viz. 94.5%, 78.5% and 1395ml/g, respectively) entailed using values of the independent variables above their mean levels. Also, ensuring optimal brightness (viz. 24.3%) required using higher temperatures and soda concentrations. A compromise that saves equipment immobilized capital and about 25% of soda is using a soda concentration of 15% at 195 degrees C for 30min. The yield thus obtained differs by less than 29.5% from the highest level; also, the resulting holocellulose content, alpha-cellulose content and brightness differ by less than 12% from their respective optimum values.     

Effect of organosolv and soda pulping processes on the metals content of non-woody pulps

In this work the effect of different pulping processes (ethyleneglycol, diethyleneglycol, ethanolamine and soda) of tow abounded raw materials (empty fruit bunches - EFB and rice straw) on the ash, silicates and metals (Fe, Zn, Cu, Pb, Mn, Ni and Cd) content of the obtained pulps have been studied. Results showed that pulps obtained by diethyleneglycol pulping process presented lower metals content (756 microg/g and 501 microg/g for EFB and rice straw pulp, respectively) than soda pulps (984 microg/g and 889 microg/g). Ethanolamine pulps presented values of holocellulose (74% and 77% for EFB and rice straw pulp, respectively), alpha-cellulose (74% and 69%), kappa number (18.7 and 18.5) and viscosity (612 and 90 6ml/g) similar to those of soda pulp, and lower lignin contents (11% and 12%).     

Characterization of vine shoots, cotton stalks, Leucaena leucocephala and Chamaecytisus proliferus, and of their ethyleneglycol pulps

We characterized vine shoots, cotton stalks, Leucaena leucocephala and Chamaecytisus proliferus as pulping raw materials and found C. proliferus and cotton stalks to be the best for the intended purpose on the grounds of their increased contents in holocellulose (79.73% and 72.86%) and alpha-cellulose (45.37% and 58.48%), and their decreased contents in ethanol-benzene extractables (2.64% and 1.42%), hot water solubles (2.79% and 3.33%) and 1% soda solubles (16.67% and 20.34%). These properties resulted in increased pulp yields and hence in efficient use of these two types of raw material. The previous raw materials were pulped by using an ethyleneglycol concentration of 65% at 180 degrees C for 75min, followed by beating at 1500 revolutions in a PFI refiner. The paper sheets obtained were characterized and those from C. proliferus found to be the best overall as they exhibited an increased breaking length (4644m), stretch (2.87%), burst index (2.46kN/g) tear index (0.33mNm(2)/g) and brightness (49.92% ISO); in addition C. proliferus pulp was obtained with a high-yield (62.88%). On the other hand, vine shoots provided the poorest results among the studied raw materials.     

Neural fuzzy model applied to ethylene-glycol pulping of non-wood raw materials

We studied the influence of the operational variables (viz. ethylene-glycol concentrations of 50-70%, temperatures of 155-185 degrees C, times of 30-90 min and numbers of PFI beating revolutions of 500-1500) on pulp yield and various paper properties (breaking length, stretch, burst index, tear index and brightness) obtained in the ethylene-glycol pulping of vine shoots, cotton stalks, leucaena (Leucaena leucocephala) and tagasaste (Chamaecytisus proliferus). The fuzzy neural network models used reproduced the experimental results with errors less than 15% and smaller than those provided by second-order polynomial models in all cases. An ethylene-glycol concentration of 65% at 180 degrees C for 75 min and 1500 PFI beating revolutions were found to provide substantial savings in energy, chemicals and facility investments as a result of operating under milder conditions than the strongest ones studied in this work. Tagasaste was found to be the most suitable raw material among those tested as it provided the paper sheets with the highest breaking length (4644 m), stretch (2.87%), burst index (2.46 kN/g), tear index (0.33 m Nm(2)/g) and brightness (40.92%); its pulp yield was also high (62.88%), which reflects efficient use of this raw material.     

Soda-anthraquinone pulping of palm oil empty fruit bunches and beating of the resulting pulp

The influence of soda-anthraquinone pulping variables (temperature, time and soda concentration) and beating (number of PFI beating revolution) of palm oil empty fruit bunches (EFB) on the resulting paper sheets was studied, with a view to identifying the optimum operating conditions. Equations were derived that reproduced the properties of the paper sheets with errors less than 10-12% in 90-95% of cases. An optimum compromise was found as regards operating conditions (15% soda, 170 degrees C, 70 min and 2400 number of PFI beating revolutions) that provided paper properties departing by less than 12% from their optimum values (59.63 Nm/g tensile index, 4.48% stretch, 4.17 kN/g burst index and 7.20 m Nm(2)/g tear index), and a beating grade of 47.5 degrees SR, acceptable to obtain paper sheets. Because these conditions involve a lower soda, temperature, time and beating than those required to maximize the studied paper properties, they can save chemical reagents, energy and immobilized capital for industrial facilities. On the other hand, the stretch properties of these pulp beaten are higher than those of others non-wood pulps, as wheat straw and olive wood.     

Bleaching of wheat straw-rich soda pulp with xylanase from a thermoalkalophilic Streptomyces cyaneus SN32

An alkalistable endoxylanase from Streptomyces cyaneus SN32 was applied in bleaching of wheat straw enriched soda pulp. The xylanase dose of 10 IUg(-1) moisture free pulp exhibited maximum bleach boosting of soda pulp (pH 9.5-10.0) optimally at 65 degrees C after 2 h of reaction time. Pre-treatment of pulp with xylanase and its subsequent treatment with 6% hypochlorite reduced the kappa number by 8.7%, enhanced the brightness index by 3.56% and improved other paper properties such as tear index and burst index. The enzymatically-prebleached pulp when treated with 10% reduced level of hypochlorite (5.4%) gave comparable brightness of resultant hand sheets to the fully bleached pulp (6% hypochlorite).     

Bleaching of soda pulp of fibres of Musa textilis nee (abaca) with peracetic acid

In this work, we studied the influence of operational variables in the bleaching of soda pulp of Musa textilis nee (abaca) [viz. temperature (55-85 degrees C), bleaching time (30-150 min) and peracetic acid concentration oven dry pulp (0.5-4.5%)] on the kappa number and viscosity of the bleached pulp, as well as on the breaking length, burst index and brightness of paper sheets made from it. For this purpose, we used a central composite factorial design in order to identify the optimum operating conditions. In this way equations relating the dependent variables to the operational variables of the bleaching process were derived. These equations reproduce the dependent variables with errors less than 12% for all, except the viscosity which was predicted with errors less than 18%. Obtaining bleached pulp with the highest possible viscosity (1519 ml/g), and paper sheets with the maximum possible breaking length (6547 m) and burst index (5.00 kN/g), entails using a temperature of 55 degrees C, a peracetic acid concentration of 4.5% and a bleaching time of 150 min. This provides a brightness of 79.90%, which is only 6.53% lower than the maximum possible value (85.48%).     

Fractionation of wheat straw by atmospheric acetic acid process

Fractionation of wheat straw was investigated using an atmospheric acetic acid process. Under the typical conditions of 90% (v/v) aqueous AcOH, 4% H(2)SO(4) (w/w, on straw), ratio of liquor to straw (L/S) 10 (v/w), pulping temperature 105 degrees C, and pulping time 3h, wheat straw was fractionated to pulp (cellulose), lignin and monosaccharides mainly from hemicellulose with yields of approximately 50%, 15% and 35%, respectively. Acetic acid pulp from the straw had an acceptable strength for paper and could be bleached to a high brightness over 85% with a short bleaching sequence. Acetic acid pulp was also a potential feedstock for fuels and chemicals. The acetic acid process separated pentose and hexose in wheat straw to a large extent. Most of the pentose (xylan) was dissolved, whereas the hexose (glucan) remained in the pulp. Approximately 30% of carbohydrates in wheat straw were hydrolyzed to monosaccharides during acetic acid pulping, of which xylose accounted for 70% and glucose for 12%. The acetic acid lignin from wheat straw showed relatively lower molecular weight and fusibility, which made the lignin a promising raw material for many products, such as adhesive and molded products.     

Bioconversion of wheat straw cellulose/hemicellulose to ethanol by Saccharomyces uvarum and Pachysolen tannophilus

The information presented in this publication represents current research findings on the production of glucose and xylose from straw and subsequent direct fermentation of both sugars to ethanol. Agricultural straw was subjected to thermal or alkali pulping prior to enzymatic saccharification. When wheat straw (WS) was treated at 170 degrees C for 30-60 min at a water-to-solids ratio of 7:1, the yield of cellulosic pulp was 70-82%. A sodium hydroxide extration yielded a 60% cellulosic pulp and a hemicellulosic fraction available for fermentation to ethanol. The cellulosic pulps were subjected to cellulase hydrolysis at 55 degrees C for production of sugars to support a 6-C fermentation. Hemicellulose was recovered from the liquor filtrates by acid/alcohol precipitation followed by acid hydrolysis to xylose for fermentation. Subsequent experiments have involved the fermentation of cellulosic and hemicelluosic hydrolysates to ethanol. Apparently these fermentations were inhibited by substances introduced by thermal and alkali treatment of the straws, because ethanol efficiencies of only 40-60% were achieved. Xylose from hydrolysis of wheat straw pentosans supported an ethanol fermentation by Pachysolen tannophilus strain NRRL 2460. This unusual yeast is capable of producing ethanol from both glucose and xylose. Ethanol yields were not maximal due to deleterious substances in the WS hydrolysates.     

Enhanced production of cellulase-free thermostable xylanase by Bacillus pumilus ASH and its potential application in paper industry

A very high level of cellulase-free, thermostable xylanase has been produced from newly isolated strain of Bacillus pumilus under submerged fermentation in a basal medium supplemented with wheat bran (2%, w/v) pH 8.0 and at 37 °C. After optimization of various production parameters, an increase of nearly 13-fold in xylanase production (5407 IU/ml) was achieved. The produced xylanase is stable in neutral to alkaline pH region at 70 °C. The suitability of this xylanase for use in the bioleaching of eucalyptus Kraft pulp was investigated. A xylanase dose of 5 IU/g of oven dried pulp of 10% consistency exhibited the optimum bleach boosting of the pulp at pH 7.0 and 60 °C after 180 min of treatment. An increase of 5% in brightness along with an increase of 21% and 28% in whiteness and fluorescence respectively, whereas 18% decrease in the yellowness of the biotreated pulp was observed. Enzyme treated pulp when subjected to chemical bleaching, resulted in 20% reduction in chlorine consumption and up to 10% reduction in consumption of chlorine dioxide. Also a reduction of about 16% in kappa number and 83% in permanganate number, along with a reduction in COD value and significant improvement in various pulp properties, viz. viscosity, tensile strength, breaking length, burst factor, burstness, tear factor and tearness were observed in comparison to the conventional chemical bleaching.     

Comparison of polynomial and neural fuzzy models as applied to the ethanolamine pulping of vine shoots

The influence of operational variables in the pulping of vine shoots by use of ethanolamine [viz. temperature (155-185 degrees C), cooking time (30-90min) and ethanolamine concentration (50-70% v/v)] on the properties of the resulting pulp (viz. yield, kappa index, viscosity and drainability) was studied. A central composite factorial design was used in conjunction with the software BMDP and ANFIS Edit Matlab 6.5 to develop polynomial and fuzzy neural models that reproduced the experimental results of the dependent variables with errors less than 10%. Both types of models are therefore effective with a view to simulating the ethanolamine pulping process. Based on the proposed equations, the best choice is to use values of the operational valuables resulting in near-optimal pulp properties while saving energy and immobilized capital on industrial facilities by using lower temperatures and shorter processing times. One combination leading to near-optimal properties with reduced costs is using a temperature of 180 degrees C and an ethanolamine concentration of 60% for 60min, to obtain pulp with a viscosity of 6.13% lower than the maximum value (932.8ml/g) and a drainability of 5.49% lower than the maximum value (71 (o)SR).     

Biobleaching of wheat straw-rich soda pulp with alkalophilic laccase from gamma-proteobacterium JB: optimization of process parameters using response surface methodology

An alkalophilic laccase from gamma-proteobacterium JB was applied to wheat straw-rich soda pulp to check its bleaching potential by using response surface methodology based on central composite design. The design was employed by selecting laccase units, ABTS (2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)) concentration and pH as model factors. The results of second order factorial design experiments showed that all three independent variables had significant effect on brightness and kappa number of laccase-treated pulp. Optimum conditions for biobleaching of pulp with laccase preparation (specific activity, 65 nkat mg(-1) protein) were 20 nkat g(-1) of pulp, 2mM ABTS and pH 8.0 which enhanced brightness by 5.89% and reduced kappa number by 21.1% within 4h of incubation at 55 degrees C, without further alkaline extraction of pulp. Tear index (8%) and burst index (18%) also improved for laccase-treated pulp as compared to control raw pulp. Treatment of chemically (CEH1H2) bleached pulp with laccase showed significant effect on release of chromophores, hydrophobic and reducing compounds. Laccase-prebleaching of raw pulp reduced the use of hypochlorite by 10% to achieve brightness of resultant hand sheets similar to the fully chemically bleached pulp.     

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.     

Positive and negative aspects of soda/anthraquinone pulping of hardwoods

The positive aspects of the non-sulfur soda/anthraquinone (SAQ) process are mostly tied to improved energy efficiency while lower pulp brightness after bleaching is its most significant drawback. A credible method that quantifies bleachability as well as an approach that solves the problem for SAQ pulps from hardwoods will be described. A straight line correlation (R2=0.904) was obtained between O2 kappa number and final light absorption coefficient (LAC) value after standardized OD0EpD1 bleaching of nine hardwood kraft pulps from three laboratories and one pulp mill. The bleachability of pulps from four different soda processes catalyzed by anthraquinone (AQ) and 2-methylanthraquinone (MAQ) was compared to that of conventional kraft pulps by comparing O2 kappa number decrease and final LAC values. It was observed that a mild hot water pre-hydrolysis improved the bleachability of SAQ pulps to a level equal to that of kraft.     

Production of conjugated linoleic acids through KOH-catalyzed dehydration of ricinoleic acid

Production of conjugated linoleic acids (CLA) using castor oil as starting material involves conversion of ricinoleic acid to methyl 12-mesyloxy-octadec-9-enoate (MMOE) followed by dehydration. This process usually uses 1,8-diazabicyclo-(5.4.0)-undec-7-ene (DBU) as an expensive dehydrating reagent. The present study reports that potassium hydroxide (KOH) can serve as a dehydrating reagent in replacement of DBU. The results showed that conversion of MMOE to CLA catalyzed by KOH was an efficient reaction, with a 77% conversion efficiency at 80 degrees C. The CLA isomeric profile produced in KOH-catalyzed dehydration reaction was similar to that catalyzed by DBU. The CLA mixture produced in KOH-catalyzed dehydration of MMOE at 80 degrees C contained 72% 9c,11t-18:2 and 26% 9c,11c-18:2 while in that catalyzed by DBU, 9c,11t-18:2 and 9c,11c-18:2 accounted for 78 and 16%, respectively. It was found that the temperature of dehydration was an important factor in the determination of CLA isomer composition and yield of conversion. Elevating the temperature from 78 to 180 degrees C decreased not only the conversion efficiency but also production of total c,t-18:2 and c,c-18:2 isomers regardless of dehydration catalyzed by either DBU or KOH. It is concluded that KOH may replace DBU as a dehydrating reagent in conversion of MMOE to CLA when the reaction conditions are optimized.     

Chemical characterization of pitch deposits produced in the manufacturing of high-quality paper pulps from hemp fibers

The composition of pitch deposits occurring in pulp sheets and mill circuits during soda/anthraquinone pulping and elemental chlorine-free pulp bleaching of bast fibers of industrial hemp (Cannabis sativa) was studied. Pitch deposits were extracted with acetone, and the extracts analyzed by gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Acetone extracts (15-25% of pitch deposits) were constituted by the defoamers used at the mill and by lipophilic extractives from hemp fibers. Acetone-insoluble residues (75-85% of pitch deposits) were analyzed by pyrolysis-GC/MS in the presence and absence of tetramethylammonium hydroxide. These residues were constituted by salts of fatty acids (arising from hemp fibers) with calcium, magnesium, aluminum and other cations that were identified in the deposits. It was concluded that inappropriate use of defoamer together with the presence of multivalent ions seemed to be among the causes of hemp extractives deposition in the pitch problems reported here.