Yoshihiro Sano

Preparation of carbon fibers from softwood lignin by atmospheric acetic acid pulping

Infusible softwood acetic acid lignin (SAL) was converted to a fusible one as a raw material for carbon fibers by removing the infusible high molecular mass fraction. The resulting low molecular mass fraction (SAL-L) was spun by fusion spinning after thermal treatment to remove volatile materials. Carbon fibers (CFs) were prepared from these fibers by direct carbonization without thermostabilization, leading to reduction of the production costs. The tensile strength of SAL-L CFs increased with decreasing diameter, and those of the fine SAL-L CFs were comparable to those of other lignin based CFs such as phenolated exploded lignin. Therefore, SAL-L CFs were classified into general performance grade.

Preparation of carbon fibers from Organosolv lignin obtained by aqueous acetic acid pulping

Lignin fibers as precursors for carbon fibers were prepared by melt spinning from organosolv lignin (AWL), which was obtained from birch wood by aqueous acetic acid pulping at atmospheric pressure and used without any chemical modification. The spinnability of AWL was attributable to polydispersity of the lignin and to partial acetylation of hydroxyl groups during the pulping. Production of satisfactory lignin fibers was achieved by simple thermal treatment of lignin, followed by continuous spinning at a rate of more than 400m/min. The thermostabilization of thin (less than 30μm in diameter) and thick threads was achieved by heating to 250°C at a rate of 0.5°C/min in air and under oxygen stream, respectively. Carbonization of thermostable fibers was achieved by heating to 1,000°C under nitrogen stream. The mechanical strength of the carbon fibers was found to be related to the diameter of fibers. Typical mechanical properties of carbon fibers from AWL were as follows : fiber diameter 14 ± 1.0 μm ; elongation, 0.98 ± 0.25% ; tensile strength, 355 ± 53 MPa ; modulus of elasticity, 39.1 ± 13.3 GPa. The carbon fibers derived from AWL can be classified as fibers of general performance grade.

Atmospheric acetic acid pulping of rice straw II : Behavior of ash and silica in rice straw during atmospheric acetic acid pulping and bleaching

Summary A detailed examination was made of the behavior and distribution of ash and silica during atmospheric acetic acid pulping and subsequent bleaching of rice straw. Ash-rich pulps (in unbleached pulp, about 18%; and in bleached pulp, 16%) with matchable strength properties for conventional alkaline pulps were obtained from rice straw by acetic acid pulping. More than 50% of the ash and about 75% of the silica in rice straw were retained in the pulp after pulping. Because only those acid-soluble mineral components were dissolved during acetic acid pulping, the ash remained in the pulp consisted mainly of silica (92.9% of the ash in unbleached pulp and 97.3% of the ash in bleached pulp). Although part of the ash dissolved during bleaching, the ash content of bleached pulp was still 15.5%, a value much higher than that in other conventional pulps. This type of ash might be good as a filler for paper. Fractionation analysis and the profile and mapping of silica by scanning electron microscope combined with an energy dispersive X-ray analysis (SEM-EDXA) indicated that the silica in the bleached pulp was located mainly in epidermal cells and not in other elements, such as fibers and parenchyma, and that the silica-rich epidermal cells were scattered throughout the pulp as single cells or in bundles.

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.

Thermomechanical analysis of isolated lignins

The thermal behavior of kraft lignin (KRL), periodate lignin (PIL), steam-exploded lignin (SEL) and acetic acid lignin (AAL), with emphasis on changes in volume upon heating, was investigated by thermomechanical analysis (TMA) in an attempt to evaluate the fusibility of lignin. All lignins underwent a glass transition but, with the exception of AAL, they all had infusible characteristics. The TMA curve for birch AAL(B-AAL) revealed two clear inflection points, assigned to the glass transition point (Tg) and the softening point (Ts) for transformation into a fluid liquid. Thus, only B-AAL among the lignins examined in this study had a fusion state. A fraction of B-AAL with almost the same weight-average relative molecular mass (Mw) as original B-AAL but with less polydispersity was found not to be transformed into a fused state. By contrast, fractions with lower relative molecular mass, namely, with Mw of less than 1,000, which accounted for 30% of AAL, had good fusibility. Therefore, the low-Mw fractions were responsible for the fusibility of B-AAL. Thermostable fusion states of acetylated KRL could not be confirmed by results of TMA and visual inspection. Thus, lignins could not be converted to fusible materials solely by the introduction of acetyl groups. Furthermore, from the results of TMA of fir AAL (F-AAL), which did not have a clear fusion state, it appeared that the fusibility of lignins was related to their molecular structures, for example, the extent of condensation of aromatic nuclei.

Activated Carbon Fibers from Acetic Acid Lignin

Activated carbon fibers (ACFs) were prepared from acetic acid lignin-based carbon fibers by steam activation. The ACF had excellent properties, such as more rapid adsorption rate and higher iodine and methylene blue adsorption capacities, as compared to a commercially available activated carbon. The adsorption mechanism of ACF was quite different from that of activated carbon (AC). as supported by the micropore distribution profiles.

Lignin gel with unique swelling property.

Lignin gels were prepared from acetic acid lignin by use of polyethylene glycol diglycidyl ether as cross-linker. The gels were found to swell in aqueous ethanol solution, in particular 50% (v/v) solution. In addition, they also swelled in alkaline solution and shrank upon heating. A literature search showed that investigation on gel swelling in aqueous ethanol has not been reported so far. Gels prepared from the cross-linker alone and its analogues did not show such swelling characteristics in aqueous ethanol. Therefore, the unique swelling property must be attributable to an intrinsic property of lignin.

Atmospheric Acetic Acid Pulping of Rice Straw IV: Physico-Chemical Characterization of Acetic Acid Lignins from Rice Straw and Woods. Part 1. Physical Characteristics

Summary Lignins obtained by atmospheric acetic acid delignification of rice straw, birch and fir were characterized by molecular weight, solubility and thermomechanical analysis, and by ultraviolet (UV), Fourier transform infra-red (FTIR) and 13C-NMR spectroscopy. Rice straw lignins (rice lignins) were very different from birch and fir lignins. The former was difficult to dissolve in most tested solvents and infusible on heating, while the latter had a good solubility and fusibility. FTIR spectra indicated that the rice lignins had more conjugated and fewer unconjugated carbonyl groups than the wood lignins. 13C-NMR spectra showed that rice lignins had more polysaccharides associated to the lignin and more p-coumaric and ferulic acid than the wood lignins. Concentrations of acetic acid and choice of catalyst (sulfuric or hydrochloric acid) had a considerable effect on the characteristics of rice lignins. Rice lignin obtained with 90% acetic acid than that obtained with 80% acetic acid, and the lignin obtained with sulfuric acid as catalyst than that obtained with hydrochloric acid, had lower molecular weight, better solubility, lower glass-transition temperature and lower UV absorptivity. 80% acetic acid delignified rice straw less effectively than 90% acetic acid.

Preparation of amphiphilic lignin derivative as a cellulase stabilizer

A polymeric amphiphile, PE-AL, was prepared from acetic acid lignin (AL) obtained by acetic acid pulping of birch under atmospheric pressure with polyethylene glycol diglycidyl ether (PE) as the crosslinker. The behavior of PE-AL solutions and the complex formation of PE-AL with protein were investigated to clarify the function of this novel lignin derivative. The reduced viscosity of the amphiphile in aqueous solution was low (<0.3dl/g), and it decreased with increasing concentration in dilute solution. This suggested that the PE-AL in aqueous solution has a structure similar to that of Einsteins sphere and shrinks upon hydrophobic interaction among the structural moieties in AL and the exclusive volume effect. The amphiphilic PE-AL obviously formed a complex with bovine serum albumin (BSA) at 4°C with a reaction time of about 1 week. After complex formation with cellulase for 1 week, the cellulase activity of the resulting complex is significantly enhanced and is preserved after recycling the complex for hydrolysis of cellulosic materials several times.

Acetic acid pulping of wheat straw under atmospheric pressure

Atmospheric acetic acid pulping of wheat straw was carried out. Pulping conditions and their effects on pulp properties were investigated in detail, and a comparison between acetic acid (AcOH) pulp and soda-anthraquinone (AQ) pulps of wheat straw was made of the chemical composition, strength, and fiber morphology of the pulps. Wheat straw was successfully pulped and fractionated into pulp (cellulose), acetic acid lignin, and sugars (monosaccharides from hemicellulose), making it easy to utilize them. It was found that among the pulping conditions the dosage of H2SO4 as catalyst was the most notable, and the extent and rate of delignification could be controlled by varying the amount of the catalyst. The results also showed that acetic acid pulp was quite different from soda-AQ pulp. About 70% of the ash or 90% of the silica in wheat straw were kept in AcOH pulp. The ash might function as filler and be beneficial to the printability of paper. It was known that many epidermal cells existed in AcOH pulp in bundles or in single cells. These ash-rich nonfiber cells seemed to hinder the bonding between fibers. AcOH pulp had lower strength than soda-AQ pulp, which might result mainly from the chemical damage of fibers caused by acid, not from the depolymerization of cellulose.