Influence of thermochemical activation of wood on the physicochemical properties of lignin

Abstract

The wood matrix is a lignin–carbohydrate nanobiocomposite, thermodynamically quasi-equilibrium heterogeneous system of biopolymers. Changing its thermodynamic equilibrium due to directed chemical and (or) physical impacts opens up new approaches to the study of plant objects. Thermochemical activation, including treatments in sub- (steam explosion) and supercritical conditions (supercritical fluid extraction) having similar mechanisms of action, is one such method. The effect of steam explosion is determined by two components — chemical (the catalytic effect of formed acetic and formic acid) and physical (a sharp adiabatic expansion). The main components of supercritical treatment are increased temperature and pressure in the CO2 medium with cosolvents. The chemical component of this treatment is due to the addition of chemical reagents. Such treatments lead to a change in the thermodynamic state and capillary-porous structure of the lignin–carbohydrate matrix, an increase in its heterogeneity, and the yield of extracted lignin preparations. Lignin is the most reactive component of the wood matrix, and these processes result in changes in its functional nature and reaction properties. Thus, the lignin sample extracted after steam explosion had the greatest increase in the content of phenolic hydroxyl (by 39 rel.%) and carboxyl (by 57 rel.%) groups. Change in the functional composition of lignin leads to a change in its redox state, characterized by the oxidative potential and free energy of oxidation. It was shown that lignin after steam explosion had the highest oxidative potential and the lowest value of the oxidation energy, which indicated the greatest change in its reactivity in redox interactions.