Phenolization of hardwood sulfuric acid lignin and comparison of the behavior of the syringyl and guaiacyl units in lignin

To study the behavior of hardwood sulfuric acid lignin (SAL) during phenolization, we compared the product yield, average molecular weight, methoxy content, and reactions of simple model compounds with those of softwood SAL, focusing on the difference between syringyl and guaiacyl units. The beech SAL reacted with phenol more readily than red pine SAL and yielded a larger soluble fraction of phenolized SAL. To investigate the difference in the phenolization activity of the syringyl and guaiacyl units in beech lignin, we prepared syringyl-nucleus-rich sulfuric acid lignin (S-rich-SAL) and guaiacyl-nucleus-rich sulfuric acid lignin (G-rich-SAL) from beech, which were subjected to phenolization. The results suggest that the syringyl unit in SAL had greater phenolization activity and its phenolized products were more soluble in acidic aqueous medium and introduced less phenol than the guaiacyl unit. Using model compounds, the study also showed that the syringyl unit had higher phenolization reactivity than the guaiacyl unit.     

Formation and chemical structures of acid-soluble lignin II: reaction of aromatic nuclei model compounds with xylan in the presence of a counterpart for condensation,and behavior of lignin model compounds with guaiacyl and syringyl nuclei in 72% sulfuric acid

To elucidate the formation and chemical structures of water-soluble material in acid-soluble lignin (ASL), lignin aromatic nuclei model compounds of creosol (I) and 5-methoxycreosol (II) were reacted with xylose or xylan in the presence of apocynol as a counterpart for condensation in 72% sulfuric acid (SA). The reaction of I gave mainly condensation product. However, the condensation reaction of II with apocynol was suppressed because of steric hindrance from the methoxyl group, and II yielded a C-xyloside after refluxing in 3% SA together with condensation products. To obtain information on CHCl₃-soluble material in ASL, model compounds of arylglycerol--aryl ethers with guaiacyl (VIII) and syringyl (X) nuclei were treated by the Klason procedure. VIII gave only insoluble polymerized product, while X gave insoluble polymerized product and CHCl₃-soluble low molecular weight products, which were dissolved in 3% SA. These results prove earlier views that water-soluble material in ASL consists of condensation products formed from syringyl lignin and monosaccharide units in hemicellulose. In addition, the CHCl₃-soluble material in ASL appears to be composed of low molecular weight degradation products from SA treatment of Klason lignin with the syringyl nucleus.Part of this report was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 2001 and at the 47th Lignin Symposium, Fukuoka, October 2002, and was reviewed in Mokuzai Gakkaishi (2002) 48:55–62     

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

Catalytic graphitization of hardwood acetic acid lignin with nickel acetate

 Catalytic graphitization of hardwood acetic acid lignin (HAL) with nickel (II) acetate was investigated regarding the production of highly crystalline carbon. Fusibility, one of the unique characteristics of HAL, was preserved with nickel acetate additions up to 0.3% (as the weight of nickel), although the thermal mobility of HAL was depressed by the addition of nickel acetate. An obvious effect of nickel salt as a catalyst on the development of carbon crystallite from HAL was observed for more than 0.2% addition. The development was found to proceed above 850°C. All the resulting carbons had turbostratic structure, and the apparent crystallite size (L _c) was increased with increasing amounts of catalyst, as determined by X-ray diffraction. Thus, highly crystalline carbon was produced from HAL by catalytic graphitization without compromising the fusibility of HAL by adding a small amount of organic nickel salt. Received: December 17, 2001 / Accepted: March 27, 2002 Present address: Department of Wood and Paper Science, North Carolina State University, NC 27695-8005, USA Part of this paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000 Correspondence to:Y. Uraki     

Sulfuric acid bleaching of kraft pulp 1: Bleaching of hardwood and softwood kraft pulps

To develop a new nonchlorine bleaching technology, hardwood and softwood kraft pulps, before and after oxygen-alkali predelignification, were treated with dilute sulfuric acid solutions (pH 1.0-1.8) at 100°C for 1 h and then extracted with aqueous sodium hydroxide at 70°C for l h. Hardwood kraft pulp was successfully bleached. The delignification selectivity was similar to that seen with oxygen-alkali bleaching; and it was greatly enhanced by the addition of sodium nitrate and sodium nitrite. The sulfuric acid bleaching can replace the presently adopted oxygen and chlorine stages if the additives are allowed. This bleaching process was also effective for oxygen-bleached hardwood kraft pulp, but it was less effective for softwood kraft pulp and oxygen-bleached softwood kraft pulp. The effectiveness of the addition of sodium nitrate and sodium nitrite was more apparent for softwood kraft pulp than for hardwood kraft pulp.Part of this report was presented at the 7th International Symposium on Wood and Pulping Chemistry, Beijing, July 1993     

Preparation of strongly acidic cation-exchange resins from gymnosperm acid hydrolysis lignin

The chemical preparation of strongly acidic cation-exchange resin from sulfuric acid lignin (Klason lignin) (SAL), a typical acid hydrolysis lignin, was investigated. Sulfonation of resinified SAL itself gave a resin with an ion-exchange capacity of 2.3 mEq/g. After resinification with formaldehyde, the phenolized SAL with a reactivep-hydroxyphenyl group yielded a resin with an ion-exchange capacity of 3.2 mEq/g. The latter capacity is superior to that of the corresponding commercial phenol-type resins (2–3 mEq/g), but did not reach the level of the corresponding commercial styrene-type resins (4-5 mEq/g).This paper was presented at the 43th Lignin Symposium, Fuchu, October 1998     

Preparation of anion-exchange resins from pine sulfuric acid lignin,one of the acid hydrolysis lignins

To utilize acid hydrolysis lignin effectively, chemical conversion to anion-exchange resin was investigated by two methods. Sulfuric acid lignin (SAL) was selected as a typical acid hydrolysis lignin in this experiment. Because it is less reactive, SAL was phenolated with sulfuric acid catalyst to yield reactive phenolized SAL (P-SAL) with p-hydroxyphenyl nuclei. One method was the restricted resinification of P-SAL followed by the Mannich reaction with formaldehyde and dimethylamine to yield a weakly basic anion-exchange resin with an ion-exchange capacity of 2.4mEq/g. Another method was to react resinified P-SAL with glycidyltrimethylammonium chloride to yield a strongly basic anion-exchange resin with an ion-exchange capacity of 2.0mEq/g. The reaction of a simple P-SAL model compound with an epoxide suggested that the phenolic hydroxyl group of the p-hydroxyphenyl nucleus had slightly higher reactivity than that of the guaiacyl nucleus.Part of this report was presented at the 47th Lignin Symposium, Fukuoka, October 2002     

Sulfuric acid bleaching of kraft pulp III: reactivity of kraft pulping-resistant structures under acidic conditions

To investigate the bleaching mechanism, a lignincarbohydrate complex (LCC) model compound, a vinyl ether-type lignin model dimer, and a hexeneuronic acid model compound were treated with dilute sulfuric acid of different pHs. Beech kraft pulp and red pine kraft pulp were also treated with dilute sulfuric acid and then extracted with aqueous alkali. The amount of hexeneuronic acid degradation products in acid effluents and lignin dissolved in alkali effluents were determined. It was found that the benzyl ether-type LCC bond and the vinyl ether bond in lignin were effectively cleaved under the pH where sulfuric acid bleaching of kraft pulp was effective. Hexeneuronic acid group was also effectively degraded during sulfuric acid bleaching. In beech kraft pulp bleaching, both lignin removal and hexeneuronic acid removal contributed to the kappa number reduction. In red pine bleaching, the contribution of hexeneuronic acid removal was negligible, and most of the kappa number reduction was achieved by the lignin removal.Part of this report was presented at the 9th International Symposium on Wood and Pulping Chemistry, Montreal, July 1997     

Chemical structures and thermochemical properties of bagasse lignin

1 Introduction Agricultural residues are an important renewable bio- mass resource. The annual production is more than 600 million tons in China. With the reduction of fossil fuel resources, the new trend is to acquire chemicals and energy from renewable resources. To produce green chemicals and clean fuels by developing bio- mass, biorefinery technology is one of the more promising technologies and objectives. Bagasse consists of cellulose, hemicellulose and lignin. Earlier studies have sho…     

Treatment of poplar callus with ferulic and sinapic acids I: incorporation and enhancement of lignin biosynthesis

Ferulic acid (FA), tetradeuteroferulic acid (DFA), sinapic acid (SA), or heptadeuterosinapic acid (DSA) was exogenously supplied to poplar (Populus alba L.) callus. Administration of FA or SA increased the lignin content of the callus to about twice that of the control callus. Gas chromatographic analysis of the alkali hydrolysate of the cell wall residue revealed that only a trace amount of SA was bound to the cell wall, and the amount of FA was less than 2% of the total callus lignin. Thioacidolysis of the DFA-treated callus indicated that DFA is effectively converted to both coniferyl and sinapyl alcohols and then incorporated into the corresponding lignin. Incorporation of DSA into syringyl lignin or guaiacyl lignin was not observed, but yields of syringyl lignin thioacidolysis products were markedly increased by DSA treatment of the callus. These results suggest that SA may not be a precursor of sinapyl alcohol and syringyl lignin per se, but it may induce or enhance the biosynthesis of syringyl lignin in poplar callus.     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate III: Successive treatment of acid hydrolysis lignin and a lignin model compound by phenolation and arylsulfonation*

The chemical conversion of red pine sulfuric acid lignin (Klason lignin) (SAL) as an acid hydrolysis lignin sample to water-soluble arylsulfonates of lignin derivation (i.e., phenolized SAL) was investigated. Treatment of phenolized SAL with chlorosulfonic acid followed by alkali hydrolysis gave water-soluble sulfonated products with a sulfonic acid group on their aromatic nuclei quantitatively. The products possess 2.0 SO₃Na/C₉ C₆. In contrast, the content of sulfuric acid group in sulfonated SAL was only 0.33C₉. Chlorosulfonation of 1-guaiacyl-l-p-hydroxyphenylethane as a phenolized guaiacyl lignin model compound revealed that the sulfonyl chloride group was introduced at thepara position of an aromatic methoxyl group, theortho position of a phenolic hydroxyl group, or both.     

Optimal germination condition by sulfuric acid pretreatment to improve seed germination of Sabina vulgaris Ant.

Understanding the germination traits of plants is important not only for understanding natural regeneration processes but also for developing seedling production techniques for planting. Sabina vulgaris Ant. is a common species used for reforestation in semi-arid areas of the Mu-Us Desert, in Inner Mongolia, China, but its extremely low germination rate, both in situ and in vivo, is a bottleneck for seedling production. Sulfuric acid pretreatment was applied to improve germination, and the germination rate was compared for different soaking time (10, 30, 60, 90, and 120 min), different temperatures (10, 15, 20, 30, and 35°C) and under different lighting conditions (dark and light). Sulfuric acid treatment gave a high germination rate, reaching 60% at 30 days after sowing. However, the non-treated seeds produced no germination. The optimal treatment time in sulfuric acid was 120 min. Germination after sulfuric acid treatment increased at incubation temperatures from 10 to 30°C, but decreased at 35°C. Incubation at 25–30°C gave maximum germination of more than 50%. Light treatment had little effect on germination. Pretreatment with sulfuric acid improved water absorption by the embryo by creating cracks and cavities in the seed coat tissue. These results indicated that S. vulgaris seeds have physical dormancy caused by their hard seed coats, which prevents absorption of water into the embryo. A combination of pretreatment with sulfuric acid and incubation at 25–30°C was most effective in improving the germination of S. vulgaris seeds.     

Preparation of activated carbon fibers with large specific surface area from softwood acetic acid lignin

Softwood acetic acid lignin (SAL) free from a high-molecular-mass fraction could be spun at 220°C by a spinning machine equipped with an extruder. Although the resulting fibers required thermostabilization, this step could be conducted with a faster heating rate than that for fibers obtained from hardwood acetic acid lignin (HAL). The thermostabilized SAL fibers were converted to activated carbon fibers (ACF) by carbonization in a stream of nitrogen at 1000°C, followed by steam activation at 900°C. At an activation time of 40 min, the SAL-ACF had a larger specific surface area than the corresponding HAL-ACF. When the activation time for SAL carbon fibers was prolonged to 80 min, the adsorption capacities of resulting ACF against iodine and methylene blue were markedly increased, as was the surface area of the ACF. It was found that SAL-ACF had adsorption properties comparable to those of high-performance commercial ACF. Also, it had a tensile strength equal to that of a pitch-derived ACF.Part of this work was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999     

Development of acid soil conditioning agent from lignin by ozone treatment I

A purified softwood kraft lignin was modified by ozone treatment and its activity as an acid soil conditioning agent, mainly focusing on elimination of aluminum toxicity, was assayed by planting experiments. The growth of radish root was examined in nutrient solution containing CaCl₂ and AlCl₃ at pH 4.8 with and without modified kraft lignins. The modified kraft lignins that absorbed 1.8 and 3.9 moles of ozone per C6-C3 unit (M _w 180) showed two effects: the elimination of aluminum toxicity and the acceleration of root growth. The effect on the elimination of aluminum toxicity was observed even with modified kraft lignin that absorbed 1.0 mole of ozone per C6-C3 unit. The high molecular weight part of the modified kraft lignin that absorbed 3.9 moles of ozone per C6-C3 unit also proved to be effective not only in elimination of aluminum toxicity but also in acceleration of root growth. The acceleration effect of ozone-treated lignins on root growth was also observed under the absence of aluminum in planting experiments. This report was presented in part at the 56th Annual Meeting of the Japan Wood Research Society, Akita, Japan, August 2006     

木质纤维成分的乙酸分离方法及表征

研究了一种用含有少量硫酸的乙酸溶液分离杨木成分的方法。考察了反应时间、乙酸浓度、液比和催化剂浓度对木材成分分离的影响。对分离出的木材三种成分进行了表征。结果表明,分离杨木成分的较佳条件为:硫酸浓度0.3%,液比6,反应时间3h和乙酸浓度90%。残渣的主要成分是α-纤维素和半纤维素。水不溶沉淀物(乙酰化木质素)的重均分子量分布在341到253之间,分散性系数分布在1.1到1.2这一窄范围内。糖分析结果表明,可溶性成分主要来源于半纤维素,以单糖形式存在。     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate II: Hydroxymethylation and subsequent sulfonation of phenolized lignin model compounds

Highly condensed lignin can be transformed by three reactions — phenolation, hydroxymethylation, and neutral sulfonation — to water-soluble lignosulfonate. To elucidate reactivities and products in the latter two reactions, simple compounds were selected as lignin model compounds. With hydroxymethylation of creosol at 60°C, the yield of a condensed-type product with the diarylmethane structure was less than 10%. Hydroxymethylation of 1-guaiacyl-1-p-hydroxy-phenylethane (compound VI) as a phenolized guaiacyl lignin model compound gave four compounds. The initial reaction introduced the hydroxymethyl group mainly in the guaiacyl nucleus, and the additional reaction created two hydroxymethyl groups in the p-hydroxyphenyl nucleus. Contrary to our estimation, treatment of the models with ¹³C-labeled formaldehyde (H¹³CIIO) did not form any diarylmethane structure. Neutral sulfite treatment of hydroxymethylated products gave corresponding sulfonates in high yields. Phenolized guaiacylglycerol--aryl ether (compound XVI) showed a reactivity similar to that of compound VI.This paper was presented at the 45th and 46th annual meetings of the Japan Wood Research Society at Tokyo and Kumamoto, April 1995 and April 1996, respectively     

Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin I: method and its application to lignin oxidation

A new method is applied to evaluate the progress of the oxidation reaction of lignin during oxygen-alkali treatment. This method employs the difference in permanganate consumption of the sample before and after the oxygen-alkali treatment as an indication for the lignin oxidation. When kraft lignin and residual lignin isolated from unbleached softwood kraft pulp were subjected to oxygen-alkali treatment up to 6000min, the progress of the oxidation expressed by this method was separated into clearly distinguished three phases. During the first and second phases, the progress of oxidation was well correlated to the loss of methoxyl group and to the decrease in the yield of nitrobenzene oxidation products. The addition of Mn⁺ to the oxygen-alkali treatment depressed oxidation during the second phase partly and that during the third phase almost completely. Calculations based on the change in the permanganate consumption revealed that the oxidation during the first phase corresponded to 4.2 electrons abstracted from one lignin structural unit on average. The oxidation process by oxygen-alkali treatment was hypothetically attributed to the direct reaction between molecular oxygen and the phenolic unit of lignin, which mainly took place during the first phase, and to the autooxidation-type oxidation during the second and third phases.Part of this paper was presented at the 9th ISWPC, Montreal, June 1997; and at the 42nd Lignin Symposium, Sapporo, October 1997     

Contribution of lignin to the reactivity of wood in chemical modifications I: influence of delignification on acetylation

In order to examine the contribution of wood components to the acetylation of wood, we acetylated wood meal that had been partially delignified. The results were analyzed in terms of the reaction kinetics. The first-order rate equation was successfully adjusted to the weight gain data. The rate constant for acetylation initially increased with progress of lignin elimination and then turned to decrease; the apparent activation energy showed the reverse tendency and ranged from about 90 to 130 kJ/mol. These results suggest that lignin elimination brings not only separation of lignin but also drastic change of the chemical and/or physical structure in the residual lignin, and this affects the reactivity of wood meal as a whole. The ultimate weight gain estimated by the regression of the rate equation showed a minimum when lignin was moderately eliminated, which was explained in terms of enhanced reactivity of lignin and lower accessibility for holocellulose than predicted. The equilibrium moisture content had a maximum when lignin was moderately eliminated. This tendency is the opposite of that observed for the ultimate weight gain, and suggests that the sites for acetylation do not always correspond to those for moisture adsorption. Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004     

Estimation of the sulfur ester content of cellulose nanocrystals prepared by sulfuric acid hydrolysis: a reproducible and fast infrared method

A fast and reproducible method for estimating the sulfur ester content of cellulose nanocrystals (CNCs) prepared by a pilot plant (Alberta Innovates Technology Futures—Alberta, Canada) is discussed. CNCs from sulfuric acid hydrolysis form electrostatically stabilized suspensions because of the introduction of sulfate ester groups onto the surface of the crystallites during the chemical production. The surface charge of the crystals and indirectly the sulfur ester content has implications when considering several applications. In the past, tedious and time-consuming methods such as X-ray photoelectron spectroscopy, X-ray diffraction, and elemental analysis have been used to estimate the sulfur content of CNCs. As of late, conductometric titrations have surpassed these techniques for estimating the sulfur content of CNC. In this communication, a technique is explored that is specific, fast, and reproducible across a number of samples for determining the quantity of C–O–S linkages in CNC samples. The method is based on integrating key peaks characteristic of sulfur functionalities obtained via Fourier transform infrared spectroscopy. The samples were analyzed as obtained, and no time was needed for extra sample cleanup prior to analysis. Finally, good correlation was obtained between the results obtained for the different samples and comparable to the results obtained from the widely used conductometric method.