Effect of temperature on the soda and kraft cooking of corn stalks

This study included soda and kraft process of corn stalks at constant active alkali, the kraft liquor having 25% sulfidity. Five cookings were made at different temperatures, 80, 120, 140, 160, and 180°C, each for 1 h. Under the condition of the study the following temperature effects were noted: (1) Delignification could be approximated by a first-order reaction. (2) The kraft process exhibited twice the rate of lignin removal as the soda of the same digestion temperature. (3) The rate of removal of carbohydrates in the kraft process is faster than soda process due to presence of sulfide ion. (4) The carbon content of thiolignin increased hydrogen and oxygen content decreased while in soda lignin the opposite occurs. (5) The amount of phenolic OH increased with increasing the cooking temperature and was more noticeable in thiolignins than in soda lignins. (6) Demethoxylation occurs in kraft cooking at elevated temperature rather than soda cooking.     

枫香树材硫酸盐制浆工艺技术研究

通过对枫香树材硫酸盐蒸煮的用碱量、硫化度、温度和保温时间四因素三水平方差分析工艺技术研究发现,在所选的四因素三水平内,用碱量对浆料得率和卡伯值的影响最大,硫化度对浆料得率和卡伯值的影响最小。枫香树材硫酸盐蒸煮较为适宜的工艺条件为:用碱量17%(Na2O计),硫化度20%,温度165℃,保温时间60 min,液比1∶6。另外,在枫香树材硫酸盐蒸煮过程中添加AQ,对提高蒸煮脱木素选择性具有明显的效果。     

Characterization of the Residual Kraft Pulp Lignin In Situ by Sulfite Treatments

Abstract

The O₂ delignification of kraft pulps from Norway spruce was shown having a significant impact on the reactivity of the residual pulp lignin as revealed from their responses to sulfite treatments at pH 7.5. A substantial higher ratio of lignin sulfonation to the phenolic hydroxyl group content of residual pulp lignin was observed for the O₂ -delignified kraft pulps (～ 0.8) as compared to a value of ～ 0.3 for the unbleached samples and ～ 1 for the spruce wood lignin. Under the prevailing sulfite treatment conditions, the sulfonation would be largely attributed to the phenolic lignin component and the etherified structures containing an α -carbonyl or -unsaturated group. The contribution from the latter units, evaluated by a borohydride pretreatment of pulps prior to the sulfite treatment, can only account for approximately 15% of the sulfonation observed for the O₂ -delignified sample. Thus, the nature of phenolic structures in the O₂ -delignified pulps was more similar to that of the wood lignin than that of the kraft pulps.     

Development of Phenolic Lignin During ClO2 Bleaching of Kraft Pulp

The development of the phenolic lignin content in kraft pulp during ClO₂ bleaching was quantitatively determined by the periodate oxidation method. The effect of hypochlorous acid, an intermediate formed during chlorine dioxide bleaching, was eliminated by addition of sulfamic acid, a scavenger of hypochlorous acid. It was found that the number of free phenolic lignin groups per 100 lignin monomer units decreased from about 29 for unbleached kraft lignin to about 6.5 after 1 minute of ClO₂ bleaching. It was also shown that the in-situ generated hypochlorous acid created phenolic hydroxyl groups during chlorine dioxide bleaching. Since it was found that delignification by chlorine dioxide itself was mostly restricted to free phenolic lignin, these findings were used to explain the effect on delignification of addition order of chlorine and chlorine dioxide during bleaching of kraft pulp.     

Delignification of Pinus taeda wood chips treated with Ceriporiopsis subvermispora for preparing high‐yield kraft pulps

Pinus taeda wood chips were treated with the white‐rot fungus Ceriporiopsis subvermispora in 20‐dm³ bioreactors for periods varying from 15 to 90 days. Decayed samples, non‐inoculated controls and extractive‐free wood samples were submitted to kraft pulping using 25% of sulfidity and different active alkali concentrations in the cooking liquor. Cooking reactions were carried out isothermally at 170 °C. Residual lignin contents of pulps prepared from biotreated wood chips were lower than those observed in pulps from the undecayed control. Delignification kinetic studies showed that the initial delignification phase was accelerated and shortened by the fungal pretreatment. At a cooking time fixed before the end of the bulk delignification phase, the fungal pretreatment provided pulps with significantly lower kappa numbers or pulps with a fixed kappa number were obtained by reducing the amount of active alkali added to the liquor. Pulps of kappa 80 were obtained both from the undecayed control cooked with 20.8% of active alkali and from the 15‐day‐biotreated sample cooked with only 15% of active alkali. The biopulping benefits were neither proportional to the extent of the biodelignification nor to the biological removal of some specific wood component. DFRC‐determination (derivatization followed by reductive cleavage) of the amount of aryl–ether linkages in residual lignins of biotreated samples indicated an extensive depolymerization during the initial stages of biodegradation, which suggested that bio‐depolymerized lignin was easily released during the first stages of cooking, resulting in a faster and shorter initial delignification phase. © 2002 Society of Chemical Industry     

A new softening agent for melt spinning of softwood kraft lignin

Kraft lignin obtained from the pulping of wood is an interesting new precursor material for carbon fiber production because of its high carbon content and ready availability. However, continuous spinning of softwood kraft lignin (SKL) has been impossible because of its insufficient softening characteristics and neat hardwood kraft lignin (HKL) has required extensive pretreatments to enable fiber formation. Softwood kraft lignin permeate (SKLP) and hardwood kraft lignin permeate (HKLP), fractionated by membrane filtration, were continuously melt spun into fibers. To improve the spinnability of SKL and HKL, HKLP was added as a softening agent. SKL‐ and HKL‐based fibers were obtained by adding 3–98 wt % HKLP. A suitable temperature range for spinning was 20–85°C above the T_g of the lignin samples, and this range gave a flawless appearance according to the SEM analysis. Smooth, homogeneous fibers of SKLP, HKLP, and SKL with HKLP were successfully processed into solid carbon fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanistic Differences Between Kraft and Soda-AQ Pulping of Hardwoods with Regard to Lignin–Carbohydrate Complexes (LCC)

The literature on biomass research contains many references to lignin–carbohydrate complexes (LCC) decreasing the rate of delignification in chemical pulping, decreasing the yield of cellulosic ethanol via fermentation, and decreasing forage digestibility. Regarding wood delignification, there are a few reports on the formation and/or cleavage of lignin–carbohydrate (L–C) bonds during alkaline pulping. The behavior of LCC was investigated to find a potential explanation for the differences between the soda-anthraquinone (soda-AQ or SAQ) and kraft processes with regard to delignification rate in the residual phase of pulping and in the bleaching process. Enzymatically isolated lignin (EL) was prepared from two soda, nine SAQ, and twelve kraft pulps from sugar maple, a hardwood. The range of kappa numbers, after correction for hexenuronic acid (HexA), was 10–60. The bound sugars on each EL were hydrolyzed and converted to monomers by H₂SO₄ at 121°C. There was evidence in the data suggesting that the bound glucan and xylan on the ELs from soda, SAQ, and kraft pulps were native to the wood. The bound galactan data were somewhat ambiguous, and there was no detection of bound mannan on any EL. The reproducibility and repeatability of bound arabinan attached to ELs (BA) were excellent. Although not conclusive, the totality of the data is suggestive of both L–C bond formation and cleavage involving arabinose units during both kraft and SAQ pulping. There was no decrease in BA when SAQ was used to lower the c-kappa number (HexA-corrected) from ～60 to ～25. The case was similar when kraft was used in the range of ～60 to ～40. However, there were significant decreases in BA content when c-kappa number was lowered below ～25 by both SAQ and kraft. A common mechanism was proposed to explain essentially no decrease in BA content at higher kappa numbers, but distinctly different mechanisms were proposed to explain BA cleavage at c-kappa number <25. A mechanism favorable to subsequent bleaching was proposed for kraft, but an unfavorable mechanism was proposed for SAQ.     

Contents of α-O-4 and β-O-4 Bonds in Native Lignin and Isolated Lignin Preparations

An analytical calculation method for the estimation of the contents of alkyl aryl ether bonds (α-O-4 and β-O-4) in lignin was developed. In the framework of the method, Alkyl–O–Aryl type bonds are described as coupled phenolic hydroxyls (OH_phen). The method is based on the balance equation including the free and coupled OH_phen contents in dissolved and residual lignins, on the one hand, and their respective contents in native lignin, on the other. The free OH_phen content is calculated on the basis of the OH_phen contents of dissolved and residual lignin, determined by the aminolysis method in the course of kraft cooking of softwood. The calculation results for soluble lignin preparations are in good agreement with the 13C NMR (nuclear magnetic resonance) spectral data for the solutions. The content of Alkyl–O–Aryl bonds in native softwood (pine, spruce) lignin was estimated at 79/100 PPU (phenylpropane unit). In isolated lignin preparations, the contents of these bonds decrease in the sequence: Freudenberg lignin (71/100 PPU)> Bjorkman lignin (61/100 PPU)> Pepper lignin (44/100 PPU). Dissolved alkaline lignin still contains small amounts of Alkyl–O–Aryl bonds (36/100 PPU in soda lignin and an average of 23/100 PPU in soda-AQ lignin, kraft lignin, and kraft-AQ lignin). Residual lignin which represents the fraction of native lignin with inter-unit bonds resistant to kraft pulping contains 66/100 PPU of such bonds. A relatively high content of Alkyl–O–Aryl bonds (61/100 PPU) is preserved in technical hydrolysis lignins.     

Kraft lignin in polyurethanes I. Mechanical properties of polyurethanes from a kraft lignin–polyether triol–polymeric MDI system

Polyurethanes with various NCO/OH ratios and kraft lignin contents were synthesized by polymerization of kraft lignin (free of the low and high molecular weight fractions), a propylene–oxide-based polyether triol and polymeric MDI in tetrahydrofuran solution. Films were made by solvent casting and tested with respect to swelling behavior and tensile properties. The main findings were: At low NCO/OH ratios, kraft lignin contributed effectively to the formation of the three dimensional network; under particular conditions of NCO/OH ratio and kraft lignin content, polyurethanes of considerable toughness were obtained; at high kraft lignin contents, the obtained polyurethanes were hard and brittle regardless of the NCO/OH ratio used.     

Molecular Mass Distribution of Lignin from the Alkaline Pulping of Hardwood,Softwood, and Wheat Straw

Abstract

The behavior of lignin during kraft (hardwood, softwood, and wheat straw) and soda-AQ (wheat straw) pulping was studied, mainly in terms of delignification degree and molecular mass distribution (MMD). In the initial delignification phase (at 140°C for 15–60 min), a prominent part of the dissolved softwood kraft lignin (18–25 g/L, MM mostly > 3,000 Da) was found in the liquid phase of chip cavities, rather than in the external bulk black liquor (5–7 g/L, MM mostly < 3,000 Da). The maximum weight average MM values ( _w) of the soluble lignin under conventional cooking conditions were detected for the kraft softwood (4,100 Da), and kraft birch (3,400 Da) when the degree of delignification was 65–75%, corresponding to a residual lignin content of 5–10%. The maximum _w of the dissolved wheat straw kraft (5,050 Da) and soda-AQ (5,900 Da) lignins was clearly higher than that of wood-based kraft lignins (2,950–4, 100 Da).     

Thermal Decomposition Study of Isolated Lignin Using Temperature Modulated TGA

Abstract

Temperature modulated TGA (MTGA) was utilized to study the kinetics of lignin pyrolysis. Three industrial lignin preparations were investigated: softwood kraft lignin, hardwood kraft lignin, and Alcell lignin. Unlike conventional TGA, MTGA provides apparent activation energy (E _a ) distribution curve using a single experimental run in a relatively short experimental time. Under Hi-Res conditions using a dynamic heating rate, the activation energies were higher than those determined using a constant heating rate. Likewise, small sample masses provided higher activation energies than those run with large sample mass. These effects can be eliminated by using a relatively large sample mass, > 10 mg. In this study, we discuss the effect of MTGA conditions on calculating E _a distribution curves for lignin pyrolysis.     

Soda Pulping of Hardwoods Catalyzed by Anthraquinone and Methyl Substituted Anthraquinones

Abstract

Black liquor gasification (BLG) as well as the recovery of lignin and other organic compounds from pulping black liquor would be aided if an efficient sulfur‐free pulping process could be developed. This has provided new impetus for research on soda pulping with redox catalysts instead of sodium sulfide that is presently used in the kraft process. Soda/anthraquinone (AQ) pulping afforded white birch (Betula papyrifera) and sugar maple (Acer saccharum) pulps with equal if not superior strength to kraft pulps. However, the delignification rate was significantly lower for soda/AQ pulping. When AQ was replaced by 2‐methylanthraquinone (2‐MAQ) a delignification rate only slightly lower than that of kraft pulping was obtained at the same effective alkali (EA). At a kappa number of ～20, a soda/2‐MAQ pulp was produced from sugar maple at a higher yield (1.2% on chips) than for a kraft pulp. 2‐MAQ was synthesized, as a powder, at 75% yield using an AlCl₃–mediated Friedel‐Crafts reaction that is one of the methods used for commercial production of AQ.     

蒸煮助剂对低用碱量硫酸盐法预处理毛竹竹屑的影响

毛竹竹屑经10%低用碱量 (以Na₂O计)、20%硫化度、160 ℃下保温1 h预处理,木质素脱除率达到62.35%,预处理物料酶水解48 h葡萄糖和木糖得率分别为56.04%和53.47%。研究了硼氢化钠、三聚磷酸钠、2-蒽醌磺酸钠3种蒸煮助剂对毛竹竹屑10%用碱量硫酸盐预处理的成分以及糖化效果影响,其中2-蒽醌磺酸钠影响最大。在10%用碱量和20%硫化度的预处理液中添加0.15%的2-蒽醌磺酸时,160 ℃下保温1 h的葡聚糖回收率和木质素脱除率分别为94.93%和68.55%,与空白对比分别提高5.45%和9.94%;预处理物料酶解48 h葡萄糖和木糖得率分别为62.88%和58.97%,与空白对比分别提高12.21%和10.29%。     

A Method for Evaluating Lignin Mobility Distributions Obtained by Capillary Zone Electrophoresis

Abstract

The profile of the mobility distribution of lignin-containing samples depends on type of sample. To facilitate comparison, a procedure for determining the average mobility (μ_av), i.e. the average charge density, of lignin is presented. The procedure is applied to black liquor (Sb), isolated dissolved lignin (Sd) and isolated residual (Sr) lignin samples, obtained from flow-through kraft cooks of softwood. The μ_av of the isolated lignin samples is compared with the concentration of phenol and carboxyl groups and relative molecular size. As the cook proceeds the μ_av for a particular type of lignin sample increases, reflecting an increase in average charge density. The μ_av, measured at pH 12, decreases in the order Sd>Sb>Sr, except at the end of the cook, when the average charge densities of the Sb and Sr samples are similar. Associations between lignin and carbohydrate fragments are proposed to cause the lower mobility of black liquor compared to isolated dissolved lignin. Characterisations performed at pH 10 indicate that the isolated dissolved lignin samples may have a higher pK_a in the middle of the cook than the other samples.     

芦苇硫酸盐浆残余木素特性的研究

从元素组成、功能基含量、结构单元三种基的比例和分子量及其分布等方面研究了苇浆残余木素的性质 ,并与芦苇木素进行了比较。研究发现 ,苇浆残余木素比起芦苇木素具有较高的氢含量和较低的氧含量 ;较低的甲氧基含量和较高的酚羟基和醇羟基含量 ;明显低的总醛含量、平均分子量及更高的多分散性。     

兴安落叶松硫化钠预处理的研究

以１００％和８０％两种硫化度的药液在相同硫化钠浓度、１５５℃下预处理兴安落叶松木片，研究了疏化度及预处理时间对预处理液硫化钠浓度、落叶松主要化学组成及木片中硫含量的影响．结果表明，在较高温度下处理落叶松，药液硫化钠浓度、木材化学组成及木片中硫含量的变化主要发生在预处理的前１小时；８０％硫化度的预处理液中由于存在一定量的氢氧化钠，对得率、木素脱除、抽提物溶出及碳水化合物的降解作用较为强烈；预处理液中硫化钠的消牦仅与初始硫化钠浓度有关，而与硫化度无关，较高的硫化度有利于木片中木素的硫化．     

Effect of irradiation on the composition and thermal properties of softwood kraft lignin and styrene grafted lignin

Lignin is an abundant, underutilized natural resource that has potential to be used as a biomaterial but is currently hampered in its use by not being uniform in structure and composition and is thermally unstable due to phenolic group. To address these issues and modify its thermal properties, softwood kraft lignin was modified using γ‐irradiation at low doses with and without styrene present and characterized. Irradiation of kraft lignin alone with γ‐radiation shows an initial decrease in molecular weight due to chain scission up to about 10 kGy followed by an increase in molecular weight due to crosslinking. NMR results indicate a decrease of about 15% in the OH content of the lignin with 30 kGy irradiation. Thermal properties such as T_g, free volume and ΔC_p follow accordingly. Irradiation at very low dosages was determined to facilitate the grafting of styrene monomer to lignin, decreasing the OH content by 23%. This effect increased the hydrophobicity of the material, depressed the value of T_g, increased the ΔC_p, increased the mobility in the liquid state, and made the material more thermally stable relative to the lignin alone, thus improving its processability at high temperatures. Both the irradiation of lignin alone and the grafting of styrene to lignin increased the yield of mass during pyrolysis and the activation energy for mass loss relative to untreated lignin alone. This work has demonstrated that the application of low dosages of γ‐irradiation is a promising method to attach functional molecules onto lignin for use in various applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39743.     

漆酶与助剂氧化体系降解苇浆残余木素的研究

用溶剂抽提法制取了苇浆残余木素 ,用漆酶 /助剂和氧气与其反应 ,通过甲氧基的测定、元素分析、1 3C -NMR、1 H -NMR和IR分析研究苇浆残余木素与漆酶 /助剂反应前后结构的变化。研究发现苇浆残余木素在反应后其甲氧基、酚羟基减少 ,醇羟基增多 ,木素结构中羰基增多 ,木素的苯环结构发生了开环反应     

蒸煮液的物理化学特征及在制浆过程中的行为 Ⅰ.离子浓度对蒸煮液的表面张力的影响

首先研究了OH-、HS-离子浓度变化对溶液表面张力的影响,然后研究了硫酸盐蒸煮液的有效碱及硫化度对溶液表面张力的影响。结果显示,c(OH-) 0.4 mol/L,c(HS-) 0.06 mol/L是蒸煮液的临界离子浓度,而有效碱浓度0.2 mol/L,硫化度20%及pH值13.65~13.70左右则是影响硫酸盐蒸煮液表面张力的临界点。     

Parameters Affecting the Cross-Flow Filtration of Dissolved LignoBoost Kraft Lignin

In the kraft pulping process, the lignin-containing by-product kraft black liquor is currently combusted as an energy source. LignoBoost is a technique that extracts lignin from kraft black liquor, resulting in a lignin-lean black liquor, which is returned to the process, and an extracted kraft lignin. To facilitate the use of the extracted kraft lignin in high-value applications, it can be refined via fractionation to produce a more homogeneous starting raw material. Hence, the aim of this study is to investigate the behavior of dissolved softwood kraft lignin during cross-flow filtration. The effects of the lignin concentration, pH, and ionic strength on the fractionation of the dissolved lignin during cross-flow filtration are investigated. The results indicate that large amounts of low-molecular-weight kraft lignin can be produced from solutions having a low lignin concentration. Furthermore, the effects of pH and ionic strength on the fractionation of low-molecular-weight lignin are identified within the studied ranges.