Oxidative cleavage of lignin aromatics during chlorine bleaching of kraft pulp
Methanol liberation and methoxyl loss during chlorine bleaching of softwood kraft pulp were quantitatively investigated to estimate the degree of structural modification of lignin aromatics. An increase in the chlorine multiple led to enhanced methoxyl loss from lignin. Our result, using pH-adjusted chlorine water (pH 5.7), by which chlorination under oxidation-favorable conditions was achieved, strongly supported the importance of the oxidation reaction by chlorine during delignification and lignin degradation. It was also suggested that methanol can be produced not only via catalytic hydrolysis by chlorine but via oxidative cleavage of the ether bond as well. The infrared spectrum of chlorolignins suggested that chlorine oxidation can open aromatic rings to muconic acid derivatives without cleaving ether bonding of the methoxyl group. No straight relation between the methoxyl content and the kappa number of chlorinated pulps was shown. The methoxyl content of bleached kraft pulps subjected to successive chlorination and alkali extraction showed a good relation with the kappa number. This means that almost all the portions of the oxidatively modified lignin structure were successfully removed during these treatments, and the aromatic structures of residual lignin in chlorinated and alkali-extracted pulps were thought to remain intact.
Novel method for the determination of the methoxyl content in lignin by headspace gas chromatography.
The paper reports on a headspace gas chromatographic (HS-GC) method for the determination of methoxyl in lignin. The method involves the quantitive cleavage of methoxyl with hydroiodic acid (HI) to form methyl iodide in a closed headspace sample vial at 130 °C for 30 min. After HI has been added, the sample is neutralized by injecting a sodium hydroxide solution; the methyl iodide in the vial was determined by HS-GC using a flame ionization detector. The results showed that the method has an excellent measurement precision (RSD < 0.69%) and accuracy (RSD < 3.5%) for the quantification of methoxyl content in lignin. The present method is simple and accurate and can be used for the efficient determination of methoxy1 content in lignin and related materials.
Thermodynamics on the Carbochlorination of Titanium-bearing Ores
The equilibrium compositions of the multi-component, multi-phase and multi-reaction system of carbochlorination of titanium-bearing ores are calculated with HSC, a computational chemistry software. The thermodynamic equilibrium calculation of the reaction system shows that a complete conversion of titanium-bearing ores is feasible at a temperature near 200oC. At temperatures ranging from 800 to 1600oC, the products of the reaction system are all in gaseous phase. Thermodynamic analysis accords with the industrial practice. The simulated results provide reasonable scientific basis for improving suitable technological conditions of the carbochlorination reduction.