Volume 8 Issue 3

Phragmites karka, a common wetland grass, was delignified by the soda pulping process, and all the operating parameters were optimized. The effects of both anthraquinone and surfactant on pulp yield and kappa number at optimum pulping conditions were also investigated. The pulp was beaten at different beating levels to optimize different mechanical strength properties. A detailed morphological study of soda-AQ pulp of P. karka was conducted by scanning electron microscopy.

Hydroxypropyl methylcellulose (HPMC)–coated papers without plasticizer and plasticized with polyols were prepared, and the effects of coating weight, different plasticizers (glycerol (GLY), sorbitol (SOR), and polyethylene glycol (PEG)), and plasticizer contents (20% to 50%) on the physical and mechanical properties of the resulting biopolymer-coated papers were studied. Coating weight was the most important factor affecting mechanical properties. Conversely, increasing coating weight led to a decrease in gloss and to an increase in tensile strength (TS), elongation at break (%E), and tearing resistance of coated papers. The application of unplasticized HPMC coatings (3 g/m2) on paper reduced water vapor permeability (WVP) and water absorption capacity by 25% as compared with uncoated paper. All plasticizers significantly (p < 0.05) increased WVP and Cobb60 values of the films. With the exception of PEG, no effect was found with plasticizers on TS and %E of coated papers compared with those without plasticizer. HPMC-coated papers with PEG as a plasticizer showed significantly lower TS and higher %E and tearing resistance than the other plasticized films (p < 0.05). HPMC coating improved tensile properties and tearing resistance of paper and could be regarded as a reinforcement layer.

The microwave liquefaction kinetics of corn stover in the presence of ethylene glycol (EG) using sulfuric acid as a catalyst was studied. The liquefaction apparent rate constant (k) was examined using a first-order reaction model. The k values of corn stover increased from 0.080 min-1 to 0.165 min-1, with the reaction temperature increasing from 120 °C to 180 °C. The k value of cellulose at 160 °C was close to that of corn stover, indicating that cellulose was involved in the rate-determining step in the microwave liquefaction. The microwave liquefaction rate of corn stover at 160 °C was seven times greater than that of conventional liquefaction with external heating. The apparent activation energy (Ea) was 22.6 kJ mol-1 and the frequency factor (A) was found to be 12.98×105 s-1. The decrease in apparent activation energy and the increase in the frequency factor as compared to conventional liquefaction kinetic parameters indicates a non-thermal effect of microwave in the liquefaction of corn stover, which explains the acceleration mechanism of liquefaction with microwaves.

In this study, Citrus sinensis (C. sinensis) solid waste was used to catalyze the conversion of free cyanide (F-CN) under alkaline conditions; conditions which represent most industrial wastewater containing F-CN. Acid hydrolysis of the solid waste increased the catalytic conversion of F-CN by 3.86 compared to the unhydrolysed solid waste. The conversion of F-CN using unhydrolysed and hydrolysed solid waste increased linearly with an increase in pH and temperature. The maximum catalytic conversion of a 100 mg F-CN/L solution containing 0.1% (w/v) of unhydrolysed and hydrolysed C. sinensis solid waste was 17.82% and 62.48%, respectively, at a pH of 12 and a temperature of 50 °C. The catalytic process was largely dependent on the availability of activated hydroxyl groups in the solid waste. As most wastewater contains heavy metals, it was determined that the presence of metallic species (Ni, Zn, and Cu) reduced the conversion of F-CN as the metallic ions attached to the hydroxyl groups. The observed reduction was 26.35% when 10 mg/L of heavy metals were present in the F-CN solution containing the hydrolysed solid waste at a pH of 12 and 40 °C.

Birch and eucalyptus kraft pulps were treated with sulfite solutions in neutral conditions (pH 7) at 170 °C for 60 min and at 190 °C for 180 min. The pulps were analyzed for kappa number, viscosity, carbohydrate composition, and optical properties. Additionally, UV resonance Raman (UVRR) spectroscopy was applied to collect information on the contents of hexenuronic acid (HexA), lignin, and its phenolic hydroxyl groups. The sulfite treatments resulted in (i) depolymerization and partial dissolution of cellulose, (ii) partial dissolution of xylan and substantial decrease in its HexA content, and (iii) removal of the major part of lignin and increase in its phenolic hydroxyl group content. The extensive removal of HexA and depolymerization of cellulose by neutral sulfite were unexpected phenomena that have not been previously reported. According to their degree of polymerization (DP), the pulps were mainly in the form of microcrystalline cellulose after the more drastic treatments.

In order to examine whether catalyst granular size was a factor for tar removal and syngas composition enhancement, three Ni/char catalysts with 90-100 mesh (Ni/SC), 50-60 mesh (Ni/MC), and 20-30 mesh (Ni/LC) size were prepared with a mechanical mixing method and tested in an updraft gasifier. Reforming parameters investigated were the reaction temperature (650-850 °C), the Ni loading (5-20% of the weight of char support), and the gas residence time (0.1-1.2 s). It was found that the catalyst granular size affected the diffusion of reactants, as well as of products. Ni/SC, Ni/MC, and Ni/LC removed more than 96.5% of the tars in syngas at 800 °C reforming temperature, 15 wt. % Ni loading, and 0.3 s gas residence time. Tar removal efficiencies increased with the decrease of Ni/char granular size, which can be attributed to the higher active surface area with the Ni/SC catalyst. As the catalyst granular size was increased, the H2 content in the syngas was increased and the CO content was significantly decreased. The total amount of combustible gases (H2, CO, and CH4) obtained in the syngas with Ni/MC was higher than with Ni/SC or Ni/LC. It was concluded that Ni/char, especially Ni/MC, can be considered as an effective and inexpensive catalyst for biomass gasification tar removal and syngas conditioning.

The feasibility of enhancing the efficiency of the kraft pulping operations while at the same time evolving the process into a biorefinery, and thus producing hemicelluloses together with paper products, was studied. Hardwood chips (Eucalyptus grandis) were pre-treatedwith green liquor prior to pulp production. At optimal pre-treatment conditions, the pH of the resulting extract was 7.8, the wood weight loss was 14%, and the hemicellulose extracted was almost 40 kg/ton of woodchips. In the subsequent kraft pulping, the resulting data revealed that the woodchips from which hemicellulose had been pre-extracted could be pulped much faster than woodchips pulped without hemicellulose extraction. As a result, to maintain the target kappa number, a 20% reduction in pulping chemicals was achievable. Hemicellulose pre-extraction led to a 10% reduction in black liquor solid contents. Moreover, the strength properties of the pulps produced with and without hemicellulose extraction were comparable. Industrial acceptance of this concept, however, still requires a more accurate understanding of the effect of specific mill operating conditions on mill energy balance. Careful economic assessment of the options for handling the calcium carbonate scale problem will also be required before the technology can be considered for implementation.

Lignin-based anion exchangers (L-AE) were prepared by reacting lignin with epichlorohydrin and triethylamine in the presence of N,N-dimethylformamide and a catalyst. A multi-factor and multi-level orthogonal design of experiment was carried out in order to obtain the optimal conditions for the preparation of lignin-based anion exchangers. The optimized parameters including the dosages of catalysts, the amounts of triethylamine, graft reaction time, and the graft reaction temperature were defined. Data of nitrate removal and yield were used as performance indicators of the products prepared. The results indicated that the reaction temperature was the primary factor. The optimal synthesis reaction parameters were lignin:pyridine:triethylamine = 2 g:3 mL:12 mL. The optimal experimental temperature was 70 °C, and the reaction time was 7 h. The yield was 188.6% and the nitrate removal was 91.2%. Under some reaction conditions, the yields were found greater than 100%; this was due to the grafted mass from epoxidation with epichlorohydrin and quaternization (through the reaction of epoxide with triethylamine).

Hydrotropic treatment is an attractive process that uses water-soluble and environmentally friendly chemicals. Currently, this method is practically unexploited on a large scale due to the long treatment times required. In this study, the hydrotropic process was modified by the addition of hydrogen peroxide, formic acid, or both. The modified treatments were more selective than the reference, and the pulps obtained using the modified treatments had lower lignin contents. After bleaching, the resultant pulps were comparable to dissolving pulps with respect to the content of hemicelluloses and viscosity. Cellulose solutions were successfully obtained in a 7% NaOH/12% urea aqueous solvent after pretreating the bleached pulp with a HCl/EtOH mixture. Hydrotropic lignin was recovered from the spent solution by precipitation in water. The lignin had very low contents of carbohydrates and sulphur. The preliminary results show that a hydrotropic process can be used for such biorefinery applications as fractionation of fibres, cellulose polymer, and lignin from birch wood. The green cellulose and lignin biopolymers can potentially be used for shaping biomaterials or production of bio-based chemicals.

In order to improve the molecular weight and application of a lignin byproduct, the trimethyl quaternary ammonium salt of lignin-sodium alginate polyampholyte (QL-SA) was prepared with trimethyl quaternary ammonium salt of lignin (QL) and sodium alginate (SA), using the cross-linker glutaraldehyde. Its structure was analyzed by FTIR, SEM, and analysis of nitrogen and carboxylic contents. Results showed that QL and SA were grafted successfully. The nitrogen content was diminished from 4.21% to 3.69% and its carboxyl content increased from 2.66 mmol/g to 6.47 mmol/g. The product behaved as flocculant by electrostatic interactions and bridging actions. The effects of QL-SA on the flocculation performance of dyes were investigated with methylene blue and acid black ATT water as the representative dyes. The maximum decolorization rate of acid black ATT was 94.91% and methylene blue was 97.11% under the corresponding optimal conditions (5 g/L of the flocculant at pH 3, 30 °C, and 8 g/L at pH 8, 30 °C). The effect of QL-SA was found to be markedly superior to SA and QL on the whole. The QL-SA showed promise for practical applications.