Interfacing spectrophotometry to process liquors applications to kraft pulping

This thesis summarizes the outcome of work performed withthe objective to contribute to the knowledge and development ofthe kraft cooking process using spectrophotometricinterfaces. In kraft cooking, it is desirable to maximize the removal oflignin in the cook without loss of pulp strength. Theselectivity can be improved by exchanging some of the hydrogensulfide ion in the white liquor for polysulfides. Paper Ipresents a spectrophotometric method for in-line monitoring ofthe electrochemical production of polysulfide using anATR-probe for the UV-Vis range. A linear relation existsbetween the ATR-probe response and the concentration ofabsorbing species. Thus the process can be followed by simplemonitoring of a few wavelengths. A spectrophotometric monitoring system using a durableNafion ionomer membrane interface for continuous on-linemeasurement of sulfide and dissolved lignin during kraftcooking has previously been developed by our group. In paperII, the permeation of low molecular weight anions from liquorshaving high ionic strengths through a membrane in Na+ form hasbeen studied. A general relation between penetration and ionsize approximated by molecular weight has been established. Thepenetration of different anions can be explained as a diffusionthrough the winding membrane channels. Further the differentanions transport independently without being interfered by thesample matrix. In light of this validation, we applied the membraneinterface to the determination of anthraquinone-2-sulfonate(AQ-S) in alkaline pulping liquor. In paper III, a simple andrapid spectrophotometric method was developed and implementedon real samples. Interferences from other compounds penetratingthe membrane were minimized by reduction of the penetrated AQ-Sand measurement at 520 nm. This method is quick and can be usedon-line. Further, we extended the method to determination ofanthraquinone (AQ) in pulping liquor (paper IV). Although AQ isregarded as insoluble, it was found that the apparentsolubility of AQ in alkaline solutions increases considerablyin the presence of lignin, reaching 0.14 g/L at 90 oC. Thismakes the calibration of AQ possible. Time-resolvedmeasurements of dissolved AQ in 3 kraft-AQ pulping processeswere performed. The results show that the membrane has great potential aspart of a selective interface in applications where theconcentrations of small anions are to be monitored in mediawith high ionic strength. Keywords: Kraft cooking, On-line, Sulfide, Lignin,Polysulfide excess sulfur, Anthraquinone-2-Sulfonate (AQ-S),Anthraquinone (AQ), Nafion Membrane, UV-Vis, ATR-probe,Spectrophotometric.NR 2014080