Effect of anthraquinone on brightness value and crystalline structure of pulp during soda processes

The dependence of crystalline structure and optical properties of pulp on anthraquinone (AQ) added to the soda process at different cooking times was determined in this study. Wheat (Triticum aestevum L.) straw was used as the raw material for pulp. Soda and soda-AQ processes were selected for pulping at 80 min and 120 min. The soda-AQ process improved the yield and viscosity of pulp delignification ratio for pulping in comparison with the soda process. Crystallinity of pulp samples decreased by adding anthraquinone to the soda process because of stabilized less ordered cellulose and amorphous hemicelluloses in pulp. It was determined that crystallinity of pulp samples decreased with longer cooking time, from 80 min to 120 min, in both soda and soda-AQ processes. Monoclinic structure was dominant in pulp samples; however, the triclinic structure ratio increased in both soda and soda-AQ processes compared to raw material. It was found that brightness and lightness values in pulp samples decreased when using anthraquinone depending on the changes of the crystalline structure.     

Infra-red spectroscopic study of lignins

Infra-red spectra from 200–4000cm⁻¹ of lignin precipitated from black liquor produced from different pulping processes of bagasse, e.g. soda, kraft, sulfite, peroxyacid and butanol, have been characterized. Peroxyacid lignins are more degraded than other lignins. However, peroxyacid lignin has a higher intensity band at 1720cm⁻¹ than other types of lignins. At the same time, the aromatic ring of lignin produced from peroxyacid pulping of bagasse undergoes severe degradation. Syringyl type of lignin is predominant in all isolated lignins. Peroxyacid and butanol lignins have lower quantities of syringyl lignin shown by the lower ratio of relative absorbance of band intensity at 1500cm⁻¹ to the band at 1600cm⁻¹ than other lignins. Kraft lignin has a broad weak band at about 630cm⁻¹ that is probably due to a C---S bond. A sharp band at 655cm⁻¹, which is due to SO₃H, is characteristic of lignosulfonate, which is precipitated from black liquor produced from sulfite pulping process of bagasse. Generally, degradation of different lignins during pulping of bagasse with different processes has the following sequence: peroxyformic > peroxyacetic > butanol-water > butanol-alkali > kraft > sulfite > soda.     

Hydrogen peroxide bleaching of cellulose pulps obtained from brewer’s spent grain

Brewer’s spent grain (BSG) was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were produced by soda pulping: one from the original raw material and the other from material pretreated by dilute acid. Both of them were bleached by a totally chlorine-free sequence performed in three stages, using 5% hydrogen peroxide in the two initial, and a 0.25 N NaOH solution in the last one. Chemical composition, kappa number, viscosity, brightness and yield of bleached and unbleached pulps were evaluated. The high hemicellulose (28.4% w/w) and extractives (5.8% w/w) contents in original BSG affected the pulping and bleaching processes. However, soda pulping of acid pretreated BSG gave a cellulose-rich pulp (90.4% w/w) with low hemicellulose and extractives contents (7.9% w/w and <3.4% w/w, respectively), which was easily bleached achieving a kappa number of 11.21, viscosity of 3.12 cp, brightness of 71.3%, cellulose content of 95.7% w/w, and residual lignin of 3.4% w/w. Alkaline and oxidative delignification of acid pretreated BSG was found as an attractive approach for producing high-purity, chlorine-free cellulose pulp.     

Displacement washing of soda rapeseed pulp

The paper deals with the displacement washing of unbleached pulp cooked from rapeseed straw by soda pulping under laboratory conditions. Pulp fibres were characterised by their average length, as well as by effective specific volume and surface. Using the step function input change method, the washing breakthrough curves measured for alkali lignin as a tracer were described by the dispersed plug flow model containing a dimensionless criterion, the Péclet number. Besides the wash yield, the dispersion coefficient as well as the mean residence time and space time were evaluated. Preliminary results obtained for soda rapeseed pulp were compared with those for kraft hardwood (beech) and softwood (spruce, pine) pulps published earlier. The wash yield measured for soda pulp was found to be lower than that for hardwood and softwood pulps which manifested lower hydraulic resistance. The presence of silique valves in rapeseed straw resulted in lower mean residence time of lignin removed from the pulp bed in comparison with pulp manufactured from stalks only.     

Structure of Alkali Lignins Fractionated from Ricinus communis and Bagasse. 1. Chemical Constituents

Fractionation of alkali lignins of the soda and sulfate pulping processes of Ricinus communis and bagasse was carried out by using successive equal concentrations of the alkaline reagent. Soda lignins were soluble in organic solvents, while the sulfate ones were sparingly soluble. Thus, two fractions of the sulfate lignins, soluble and insoluble, could be obtained from acetone. The different alkali lignin fractions were subjected to elemental and functional group analyses. For both Ricinus communis and bagasse, the carbon content of the fractions of the various types of lignin is in the order: soluble sulfate > soda > insoluble sulfate, while the methoxy is in the order: soda > soluble sulfate > insoluble sulfate. The phenolic OH content, as well as OH/C₉ of soda lignins of bagasse, are lower than those of soluble sulfate lignins. For Ricinus communis, the phenolic OH content and OH/C₉ is higher for some of the fractions (first three stages of cooking) of soda lignin than the corresponding fractions of kraft (sulfate) lignin, while the reverse takes place for the other fractions. For the same type of lignin, the fractions showed changes in their carbon, methoxyl, and phenolic OH contents. The change may be regular, i.e., increase or decrease with the order of stage of cooking, or irregular. Molecular weights of the different alkali lignins which are soluble in organic solvents ranged between 750 and 840.     

Chemical,Thermal and Antioxidant Properties of Lignins Solubilized during Soda/AQ Pulping of Orange and Olive Tree Pruning Residues

Some agroforestry residues such as orange and olive tree pruning have been extensively evaluated for their valorization due to its high carbohydrates content. However, lignin-enriched residues generated during carbohydrates valorization are normally incinerated to produce energy. In order to find alternative high added-value applications for these lignins, a depth characterization of them is required. In this study, lignins isolated from the black liquors produced during soda/anthraquinone (soda/AQ) pulping of orange and olive tree pruning residues were analyzed by analytical standard methods and Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (solid state ¹³C NMR and 2D NMR) and size exclusion chromatography (SEC). Thermal analysis (thermogravimetric analysis (TGA), differential scanning calorimetry (DSC)) and antioxidant capacity (Trolox equivalent antioxidant capacity) were also evaluated. Both lignins showed a high OH phenolic content as consequence of a wide breakdown of β-aryl ether linkages. This extensive degradation yielded lignins with low molecular weights and polydispersity values. Moreover, both lignins exhibited an enrichment of syringyl units together with different native as well as soda/AQ lignin derived units. Based on these chemical properties, orange and olive lignins showed relatively high thermal stability and good antioxidant activities. These results make them potential additives to enhance the thermo-oxidation stability of synthetic polymers.     

Ceriporiopsis subvermispora used in delignification of sugarcane bagasse prior to soda/anthraquinone pulping

Sugarcane bagasse was pretreated with the white-rot fungus Ceriporiopsis subvermispora for 30 d of incubation. The solid-state fermentation of 800 g of bagasse was carried out in 20-L bioreactors with an inoculum charge of 250 mg of fungal mycelium/kg of bagasse. The oxidative enzymes manganese peroxidase (MnP), lignin peroxidase (LiP), and lac-case (Lac) and the hydrolytic enzyme xylanase (Xyl) were measured by standard methods and related to the fungus’s potential for delignification. Among the lignocellulolytic assayed enzymes, Xyl was detected in larger quantity (4478 IU/kg), followed by MnP (236 IU/kg). LiP and Lac were not detected. The results of chemical analysis and mass component loss showed that C. subvermispora was selective to lignin degradation. Pretreated sugarcane bagasse and control pulps were obtained by soda/anthraquinone (AQ) pulping. Pulp yields, kappa number, and viscosity of all pulps were determined by chemical analysis of the samples. Yields of soda/AQ ranged from 46 to 54%, kappa numbers were 15–25, and the viscosity ranged from 3.6 to 7 cP for pulps obtained from pretreated sugarcane bagasse.     

Xylanase and Ultrasound Assisted Pulping of Wheat Straw

In the present work, a novel approach to pretreat wheat straw pulping was investigated with ultrasound and xylanase to achieve maximum reduction in lignin content. Sequential xylanase pretreatment and alkaline pulping was found to reduce kappa number by 0.31 to 4.84?% compared with only alkaline pulping alone at different pulping conditions. Although Klason lignin of ultrasound-treated straw was found to be 7.37?% less compared with untreated straw, sequential ultrasound pretreatment and alkaline pulping could not show any significant reduction in kappa number compared with alkaline pulping alone. Also, sequential xylanase and ultrasound pretreatment could not show any significant reduction in kappa number. Total yield of the pulp was found to be less in ultrasound-assisted processing compared with both alkaline pulping alone and sequential xylanase pretreatment and alkaline pulping.     

苛性碱、碳酸碱和全碱的同时流动注射分析

采用流动注射滴定技术实现了氧化铝生产过程中铝酸钠溶液中苛性碱、碳酸碱和全碱的同时自动分析。以磺基水杨酸为载流,它既为滴定剂又是铝的掩蔽剂;酚酞和甲基橙混合液为试剂流,它们是苛性碱、碳酸碱和全碱的指示剂。该法可测定６．２～３０．９ｇ／Ｌ的碳酸碱和３．１～１５．５ｇＬ的苛性碱（均以Ｎａ２Ｏ计）,测定速率３０个样／ｈ,标准标准偏差小于０．５％（ｎ＝１１,Ｎａ２Ｏ＝２１．９４ｇ／Ｌ）。     

Significance of fatigue for mechanical defibration

The fatigue induced by high-frequency cyclic loading on the compressibility and tensile properties of wood and wood cell walls was quantified. The non-elastic behavior of fatigued and reference samples was similar, whereas their elastic behavior differed, as expected. Next, the effects of the dynamic fatigue on the mechanical pulping process were quantified by grinding fatigued and untreated samples and by comparing the paper strength produced by the two pulps against the consumed pulping energy. Pre-introducing fatigue increased the energy efficiency of grinding and may allow designing a more energy efficient mechanical pulping process.     

The influence of soda additive on the thermal properties of red mud

The dehydration and decomposition of the red mud from Seydięehir Aluminum factory, mixed with soda were investigated under dynamic and isothermal conditions. Soda was added to the red mud samples as much as 50, 100 and 150 mass% of Na₂CO₃ of the red mud sample's mass. To determine the effect of soda additive on the red mud's thermal properties, using TG and DTA techniques simultaneously under atmospheric conditions. Furthermore, the original red mud sample's XRD and IR spectrum curves were investigated. It seems that the temperatures of the endothermic peaks of the red mud decreased with the amount of soda added. However the endothermic peak's temperature readings showed that the melting of soda increased gradually with the quantity of soda used. This revised version was published online in July 2006 with corrections to the Cover Date.     

The thermal behaviour of lignins from wasted black pulping liquors

The thermal degradation of lignins separated from black liquor waste from pulping of bagasse and cotton stalks has been investigated. Thermal gravimetric analysis (TGA), differential thermal analysis (DTA) and derivative thermogravimetry (DTG), between 20 and 1000°C, have been used. Activation energies of treated lignins were calculated. Lignins separated from liquors obtained at low pulping temperature have higher activation energies than high-temperature lignins. The use of anthraquinone (AQ) as an additive for accelerating the pulping process raises the activation energy of the lignin in the black liquors waste.     

凝胶渗透色谱法对桉木过氧化氢化学法化学机械浆制浆过程木素分子量变化的机理研究

利用凝胶渗透色谱法和元素分析法测定了尾叶桉酶解木素在过氧化氢化学法化学机械浆(APMP)制浆及漂白过程分子量的变化.研究结果表明:由于HOO的特殊作用制浆及漂白之后,浆中剩余木素的平均分子量相对有所增加.     

Formulation of an Environmentally Friendly Adhesive for Wood

Summary: Malaysia has over 4 million hectares of oil palm plantations that yield large amounts of empty fruit bunches (EFB) generated from palm oil milling operations. These forms of lignocellulosic residue pose an environmental hazard if their disposal is not managed in a systematic manner. One of the useful elements extracted from these EFBs is lignin. The general purpose of this study is to explore the potential uses of lignin extracted from soda black liquor (paper and pulping waste) derived from oil palm empty fruit bunches (EFB) in the formulation of a more environmentally friendly wood adhesive. In this work, the potential for replacing phenol with lignin in phenol formaldehyde resin formulation is examined. The quantity of phenol was reduced by synthesizing the resin at a lignin to phenol ratio of 1:1. The physical and chemical properties of lignin phenol formaldehyde resin (LPF) and commercial phenol formaldehyde resin (CPF) were then compared. The infrared spectrum revealed similarities in the functional groups of both LPF and CPF resins. Tensile strength comparisons between both resins revealed that the LPF resin had a higher bonding strength (11.60 MPa more in term of allowable maximum load). In addition, the kinematics viscosity test showed that the LPF resin had lower kinematic viscosity than the CPF resin after 21 days of storage. Finally, the scanning electron microscope images for both resins showed similarities in terms of penetration into wood vessels.     

Evaluation of new organosolv dissolving pulps. Part I: Preparation, analytical characterization and viscose processability

New acidic organosolv pulping processes, such as Acetosolv, Formacell and Milox, promise to have superior potential in terms of purification selectivity and specific investment costs. Consequently, a thorough investigation of these new acidic pulping processes in comparison to state-of-the-art acidic magnesium sulfite technology was conducted. The impact of pulping and bleaching parameters on the physical and chemical characteristics was studied to compare process efficiency and selectivity for each type of pulp made from Eucalypt wood. In addition to a detailed analysis of the chemical composition and physical properties on a molecular and supramolecular level, the TCF-bleached dissolving pulps were tested for their applicability in viscose fiber production. The influence of pulp properties as determined by standard and advanced analytical methods on process performance and selected fiber properties is emphasized.     

Lignin depolymerization for phenolic monomers production by sustainable processes

Biomass wastes(almond shell and olive tree pruning) were used in this work as raw materials for the extraction of high purity lignin by different delignification methods. A pretreatment stage was carried out to remove the major hemicelluloses content in the solid feedstocks. Afterward, two sulfur-free pulping processes(soda and organosolv) were applied to extract the largest fraction of lignin. The extracted lignin contained in the liquors was isolated using selective precipitation methods to design a tailor-made technique for obtaining high-purity lignin(in all cases more 90% of purity was reached). Soda process allowed the extraction of more lignin(around 40%–47%) than organosolv process(lower than 20%) regardless of the lignocellulosic source employed.Once the different lignin samples were isolated and characterized, they were depolymerized for the obtaining of small phenolic compounds. Three main streams were produced after the reaction: phenolic enriched oil, residual lignin and coke. After the purification of these fractions, their quantifications and characterization were conducted.The most abundant product of the reaction was residual lignin generated by the undesirable repolymerization of the initial lignin with yields around 30%–45%. The yield of the stream enriched in phenolic oil was higher than 20%. Coke, the lowest added-value product, presented a yield lower than 12% in all the cases. Lignin from organosolv presented higher phenolic oil yields, mainly due to their lower molecular size. This parameter was, thus, considered a key factor to obtain higher yields.     

Reaction of xylan with aqueous solutions of alkali

Conclusions 1. The action of an aqueous solution of caustic soda on xylan leads to the formation of both a molecular and an alkoxide form of this polysaccharide. The composition and amount of the alkoxide formed depend on the conditions of treating the xylan with alkali.2. In the reaction of an aqueous solution of caustic soda with xylan, the hydrogen of the alcohol grouping on the second carbon atom exhibits the greatest reactivity.3. The result of IR spectroscopy confirm the existence of a chemical interaction of the xylan with caustic soda.4. According to X-ray analysis, the action of a solution of caustic soda on xylan leads to a decrease in intermolecular interaction, to a more ordered supermolecular structure, and to the appearance of crystallinity.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 4, pp. 206–210, 1969     

Pulp depitching in the bisulfite pulping step

OS-20 nonionic surfactant produced in Russia was used as a depitching additive in bisulfite pulping. OS-20 ensures efficient depitching of bisulfite pulp produced from various kinds of wood (spruce, aspen, birch wood or their blends). The strongest decrease in the total and “harmful” pitch content in pulping in the presence of the surfactant was reached for spruce and aspen wood and for the blend of spruce and birch wood.     

Preparation and Properties of HBS Lignin from Masson Pine

In order to establish a new method for making cellulose and lignin from Masson pine, a high boiling solvent (HBS) pulping process with an aqueous solvent of 1,4-butanediol was investigated. Masson pine chips were pulped with a 70%--90% aqueous solution of 1,4-butanediol containing a small amount of a catalyst at 200--220℃ for 60--180 min. HBS Masson pine cellulose is suitable for making paper. Water-insoluble HBS lignin was separated from the liquor reaction mixture by water precipitation. The recovered high boiling solvent (RHBS) is able to be recycled as a pulping solvent, indicating that the HBS method is a pulping process of Masson pine which is energy saving, resources saving and pollution free. HBS lignin has a better chemical reactivity and a lower ash content than lignin sulfonate.     

Effect of urea on cellulose degradation under conditions of alkaline pulping

The effect of urea on the cellulose degradation under conditions of alkaline pulping has been studied using purified cellulose powder. The increased cellulose yield in the presence of urea was assigned essentially to the carbamation reactions which were confirmed by elemental analysis, UV-resonance Raman and solid-state ¹³C nuclear magnetic resonance spectroscopy. The stabilizing effect of urea on the cellulose peeling reactions during heating up period of pulping process was suggested based on kinetic studies and additionally confirmed in model reactions using cellobiose. The reaction products formed in alkaline urea solutions were analysed by tandem electrospray ionization mass spectrometry and the occurrence of Maillard type reactions between reducing end groups of cellobiose and urea were evidenced. Both Maillard type reactions and carbamation of reducing end groups were proposed to be a part of cellulose protection mechanism against peeling under the conditions of alkaline pulping.