Abstract:
The H
5PV
2Mo
10O
40 heteropoly acid was prepared by the conventional methods and was characterized with FT-IR, XRD and SEM. InH
5PV
2Mo
10O
40+BMIMCl dual function catalytic system and BMIMCl single function catalytic system, the effects of reaction time, reaction temperature and the amount of H
5PV
2Mo
10O
40 on the lignin degradation process were studied, and the degradation mechanism was also discussed preliminarily. The results indicated that the contents of P, V, Mo in the synthesis H
5PV
2Mo
10O
40 heteropoly acid accorded with the relationship of 1:2:10, and the H
5PV
2Mo
10O
40 heteropoly acid had the typical Keggin structure.Under the optimal reaction condition, i.e., 140 ℃, 3 hours, the ionic liquids were used as the catalysts, the contents of total hydroxyl of alkali lignin increased from 3.49 to 10.92 mol/kg after reaction, and the mass fraction of vanillin and syringaldehyde were 2.00% and 2.15% in liquid products, respectively. When 20% H
5PV
2Mo
10O
40 was added, the optimal reaction time and temperature were 6 hour and 120 ℃, and the total hydroxyl increased from 3.49 to 14.12 mol/kg in solid degradation products. The molar mass reduced from 7.691 to 1.589 kg/mol. Only vanillin was found in liquid products, and its mass fraction was 6.97%. It was believed that H
+ attacked oxygen atom on the
β-O-4 bond in lignin firstly when BMIMCl catalyzed lignin alone. At the same time, the positive charge was transferred to the
β position, and then the oxygen atom in the water molecule attacked the
β position which had positive charge. As a result, catalyst H
+ was eliminated and
β-O-4 bond generated guaiacol due to the hydrolytic cleavage. Then the side chain generated vanillin and syringaldehyde by the oxidation reaction. When H
5PV
2Mo
10O
40 was added, PV
2Mo
10O
405- released VO
2+ and its valencestate was changed from V(V) to V(IV). The single electron oxidation model compounds were obtained and the lignin was demethylated. It was thought that the lignin demethoxy group was changed from lignin-type lignin to guaiacol-type lignin, not only without any clove aldehydes were found in the liquid product but also the contents of vanillin were increased.