Spectroscopic evidence of silica-lignin complexes: implications for treatment of non-wood pulp wastewater

This research examined the hypothesis that lignin compounds form aqueous complexes with silica increasing its solubility, thereby inhibiting its precipitation. An experimental program using four lignin model compounds was conducted to test the hypothesis. Laser Raman spectroscopy (LRS) was used to characterize, qualitatively, the interaction between lignin and aqueous silica, and to identify the possibility of silica-lignin complexation. Solubility studies were then performed by analyzing the solubility of silica in presence and absence of lignin within the relevant pH range to confirm the results of LRS, and to obtain a quantitative assessment of the relative solubility. The findings have established the formation of silica-ferulic, silica-vanillic, and silica-4-methoxycinnamic acid complexes, but no evidence was detected for the formation of silica-veratryl alcohol complex. In fact, the black liquor undoubtedly contains much more complex lignin materials than the simple model compounds used in this work. The more complex lignin compounds are likely to have an even greater tendency to form silica complexes, thus contributing to the initial hypothesis. This finding provides a fundamental understanding as to why previous efforts to precipitate silica by lowering the pH from 10-11 (for black liquor) to less than 9 did not achieve satisfactory silica separation, and why alternative strategies need to be investigated.