Dissolved and Colloidal substances (DisCo) and metals are released from wood during thermomechanical pulp (TMP) production. The mechanical treatment causes that these components have a tendency to accumulate in process waters, as the water circulation systems in integrated paper mills are being closed. Disturbances such as pitch depositions on the paper machine (pitch problems), specks in the paper, decreased wet and dry strength, interference with cationic process chemicals, and impaired sheet brightness and friction properties appear in the presence of DisCo substances. The presence of transition metal ions such as manganese results in higher consumption of bleaching chemicals (hydrogen peroxide) and lowers the optical quality of the final product, and addition of complexing agents, such as EDTA or DTPA, to prevent this is needed. The never ending trends to decrease water consumption and increase process efficiency in pulp and paper production stress that it is very important both to know the effects of wood substances on pulping and papermaking and to be able to remove them in an efficient way. Carried out investigations presented in this thesis show that the lipophilic extractives can be removed from TMP press water to high extent. A 90% decrease in turbidity and a 91% removal of lipophilic extractives from TMP press water can be obtained by addition of a cationic surfactant as foaming agent during flotation. Additionally, fibres located in TMP press water are not removed with the foam fraction but purified. A retained concentration of hydrophilic extractives in the process water indicates that the flotation is selective. Moreover, by introduction of a new recoverable surface active complexing agent, a chelating surfactant, manganese ions in the form of chelates can be successfully removed from the pulp fibres and separated from the process water in the same flotation process. iii The findings presented above indicate new possibilities for internal water cleaning and decreased emissions to water if flotation technology is applied in an integrated mechanical pulp mill. / ReGain/FORE

Dissolved and Colloidal substances (DSC) and metals are released from woodduring thermomechanical pulp (TMP) production. These components have atendency to accumulate in process waters, as the water circulation systems inintegrated paper mills are closed. Disturbances such as pitch depositions in thepaper machine (pitch problems), specks in the paper, decreased wet and drystrength, interference with cationic process chemicals, and impaired sheetbrightness and friction properties appear when DSC are present. Transition metalions such as manganese results in higher consumption of bleaching chemicals(hydrogen peroxide) and lowers the optical quality of the final product, andaddition of complexing agents, such as EDTA or DTPA, to prevent this is needed.The never ending trends to decrease water consumption and increase processefficiency in pulp and paper production emphasizes that it is very important bothto know the effects of wood substances on pulping and papermaking and to beable to remove them in an efficient way. From a biorefinery point of view, DSCcomponents can be promising renewable raw materials for biofuels, bio‐basedchemicals and materials.In this thesis, a new approach using induced air flotation (IAF) without a cationicpolyelectrolyte addition for the removal of pitch and metal ions from mechanicalpulp mill process waters is presented. The induced air flotation of different processwaters is facilitated by the addition of a chelating surfactant and different foamingagents. The influence of the pH value, temperature and foaming agentconcentration on the flotation efficiency has been investigated. The investigations presented show that the disturbing components can be removed from TMP presswater to a high extent. A 90% decrease in turbidity and a 91% removal of lipophilicextractives (i.e. resin and fatty acids, triglycerides, sterols and steryl esters) fromunbleached and bleached TMP process water can be obtained by addition of acationic surfactant as foaming agent during flotation. Lower amount of foamingagent is needed to purify efficiently bleached TMP process water, than unbleached.Additionally, fibres located in TMP press water are not removed with the foamfraction but purified. A retained concentration of hydrophilic extractives (i.e.hemicelluloses and lignans) in the process water indicates that the flotation isselective. Moreover, by introduction of a new recoverable surface activecomplexing agent, a chelating surfactant, manganese ions in the form of chelatescan be successfully removed from the pulp fibres and separated from the processwater in the same flotation process. Furthermore, from the purified unbleachedTMP process water a 90% recovery of dissolved hemicelluloses by anti‐solventprecipitation was obtained.The findings presented above indicate new possibilities for the internal watercleaning stage to decrease DSC emissions to recipient and for recovery of valuableraw materials from purified process water if flotation technology is applied in anintegrated mechanical pulp mill. / FORE

The purpose of this study was to investigate the fundamental characteristics of a chelating surfactant in terms of solution behaviour, chelation of divalent metal ions, and interaction in mixtures with different foaming agents and divalent metal ion, as well as examining its prospects in some practical applications. Chelating surfactants are functional molecules, with both surface active and chelating properties, which are water soluble and therefore suitable for chelation in many aqueous environments. The dual functionality offers the possibility to recover the chelating surfactant as well as the metals. The DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 4-C12-DTPA (2-dodecyldiethylenetriaminepentaacetic acid) was synthesized at Mid Sweden University. In the absence of metal ions, all eight donor atoms in the headgroup of 4-C12-DTPA are titrating and the headgroup charge can be tuned from +3 to -5 by altering the pH. The solution properties, studied by surface tension measurements and NMR diffusometry, were consequently found strongly pH dependent. pH measurements of chelating surfactant solutions as a function of concentration was used to extract information regarding the interaction between surfactants in the aggregation process. Small differences in the conditional stability constants (log K) between coordination complexes of DTPA and 4-C12-DTPA, determined by competition measurements utilizing electrospray ionization mass spectrometry (ESI-MS), indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. This was further confirmed in hydrogen peroxide bleaching of thermomechanical pulp (TMP) treated with 4-C12-DTPA. Interaction parameters for mixed systems of 4-C12-DTPA and different foaming agents were calculated following the approach of Rubingh’s regular solution theory. The mixtures were also examined with addition of divalent metal ions in equimolar ratio to the chelating surfactant. Strong correlation was found between the interaction parameter and the phase transfer efficiency of Ni2+ ions during flotations. Furthermore, a significant difference in log K between different metal complexes with 4-C12-DTPA enabled selective recovery of the metal ion with the highest log K. The findings in this study contribute to the understanding of the fundamental characteristics of chelating surfactants, which can be further utilized in practical applications.