Abstract
To the value-added application of the soda lignin by improving its reactivity and antioxidant activity, a self-made Pd/SO42−/ZrO2 catalyst was used to catalyze the degradation reaction of soda lignin. The catalyst was loaded with the palladium of 1.47 wt.% while retaining the super acidity of SO42−/ZrO2. The reaction condition was determined as follows: the dioxane-water solution was selected as the reaction solution, the addition amount of the catalyst was 5 wt.% of the soda lignin, the system was heated at 100 °C for 4 h under a hydrogen pressure of 3 MPa. The reactivity of the catalyzed-soda lignin compared to the soda lignin before the reaction was significantly improved: the values of phenolic hydroxyl groups and total hydroxyl groups were increased by 35.3% and 97.1%, respectively, and the value of methoxy groups was decreased by 13%. Approximately 63.3% of the β-O-4 bonds were cleaved, which resulted in a reduction of the weight average molecular weight from 8200 g·mol−1 to 4900 g·mol−1. At the same time, the EC50 values of the catalyzed-soda lignin on DPPH (1,1-diphenyl-2-picrylhydrazyl) and ABTS+ (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) radicals scavenging were decreased by 20.6% and 32.6%, respectively, and the reducing power of catalyzed-soda lignin at the absorption value of 0.5 was increased by 10.5%. The Pd/SO42−/ZrO2 catalyst works by breaking the β-O-4 linkages and degrading the methoxy groups. The catalyzed-soda lignin exhibits the possibility of being used as the antioxidants, grafting precursors, adhesive additives, and raw materials for lignin/polymer composites.
Highlights
Soda lignin is a type of technical lignin derived from the black liquor
The reactivity of the catalyzed-lignin was improved in the reaction, and we found that the antioxidant activity of catalyzed-lignin was improved
For the Pd/SO4 2− /ZrO2 catalyst, the weak acid sites appeared at 140 ◦ C, and the medium-strong and strong acid sites appeared at 450 ◦ C and 600 ◦ C, respectively
Summary
Due to the high degree of polymerization and low reactivity, the soda lignin is difficult to be utilized. Soda lignin consists of three structural units, such as the guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H) units, and it contains some active functional groups. Soda lignin may hopefully be used as a raw material for synthetic fine chemicals or lignin-based polymers. In comparison, improving the reactivity of lignin is another effective method for its value-added utilization [4]. We developed some acid catalysts and hydrocracking catalysts to degrade the β-O-4 bond of lignin under relatively mild conditions. The reactivity of the catalyzed-lignin was improved in the reaction, and we found that the antioxidant activity of catalyzed-lignin was improved
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