The Use of Cationites in the Modification of Kraft Lignin with Nitrous Acid
DOI:
https://doi.org/10.37482/0536-1036-2025-6-155-168Keywords:
lignin, kraft lignin, modification, modified lignin, nitrous acid, nitrosation, solidphase catalysis, electron spectroscopy, infrared spectroscopyAbstract
Kraft lignin is the largest-tonnage technical lignin formed during kraft pulp cooking. According to statistics, approximately 70 mln t of such waste are generated annually. Most of it is disposed of in the system of chemicals recovery and thermal energy generation. Approximately 10…20 % of kraft lignin can be used to obtain a variety of products, for example, in the production of polymers, low-molecular compounds, activated carbon production, rubber industry, etc. For this purpose, kraft lignin is subjected to various types of modifications, including chemical ones: periodate oxidation, halogenation, sulfonation, sulfomethylation, nitration, nitrosation, etc. This article presents a new method for modification of kraft lignin with nitrous acid in a water-dioxane medium using solid-phase catalysis. The cation-exchange resins in H-form containing sulfogroups (cationite KU-2-8 and wofatite) have been used as catalysts. The optimal reagent consumption has been determined to be 50 % sodium nitrite and 230 % cationite from kraft lignin. It has been shown that the developed method and the well-known one using sulfuric acid as a catalyst give similar results. The molecular and electronic spectra of modified kraft lignin have been studied. In the electronic spectra of modified kraft lignin, a new absorption band appears characteristic of the nitroso group in the region of 400…500 nm with a maximum at 451 nm. By deconvolution, the electronic spectrum of modified kraft lignin is approximated by 6 Gaussians with an error of 2.5 %, while for the initial kraft lignin the spectrum can be described by 4 Gaussians with an error of 3.4 %. In contrast to the IR spectrum of kraft lignin, new absorption bands appear in the spectra of modified lignin at 615, 760, 1,330 and 1,550 cm–1, which are due to vibrations of NO bonds.
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