Mid Sweden University

Lignocellulose biomass plays an important role in reducing thedependency on fossil fuels and ameliorating the dire consequences ofclimate change. It is therefore important that all the components oflignocellulose biomass are exploited. These components includehemicelluloses and extractives that are liberated and sterically stabilizedduring the thermomechanical pulping and that form the dissolved andcolloidal substance (DCS) in the process water. Biorefining of this processwater can extract these substances, which have a number of promisingapplications and can contribute to the full exploitation of lignocellulosebiomass. This paper presents a simple treatment of unbleached Norwayspruce (Picea abies) process water from TMP (thermomechanical pulping)production using induced air flotation (IAF) and cationic surfactant,dodecyl trimethylammonium chloride (DoTAC) to refine the extractivesand prepare the waters so that hemicellulose could be easily harvested ata later stage. By applying 80 ppm of DoTAC at a pH of 3.5 and 50 °Cbefore induced air flotation, 94% of the lipophilic extractives wererecovered from process water. Dissolved hemicellulose polysaccharideswere cleansed and left in the treated process water. The process enabledefficient biorefining of lipophilic extractives and purification of the processwater to enable more selective harvesting of hemicelluloses in subsequentsteps.

During the thermomechanical pulping (TMP) of spruce, hemicelluloses (mainly galactoglucomannans, GGMs) are released into the process water at relatively low concentrations that are currently impossible to efficiently recover. This paper examines the recovery of hemicelluloses precipitated from TMP process water via solubility reduction by adding antisolvents such as methanol, ethanol, and acetone. The phase separation was monitored by turbidity measurements. Gravimetric analysis, FTIR, GC–MS, UV spectroscopy, and ICP-OES were used to determine the yield, purity, and composition of the precipitates. Gel permeation chromatography and pulsed field-gradient self-diffusion NMR were used to measure the molecular mass distribution of the precipitates. Acetone was found to be the most efficient antisolvent, giving the highest yield at the lowest addition. The contents of lipophilic extractives and lignin impurities were below 0.5% and 1.6%, respectively, and the metal content was approximately 2% in the precipitates obtained with acetone.

The environmentally benign closure of water systems in paper mills leads to the problem of accumulation of dissolved and colloidal wood substances (DCS) in process water. Notably, pitch affects the pulp and paper production negatively and increases the demand for additional treatment of the process water. In the present article, the purification of thermomechanical pulping process water from the alkaline peroxide bleaching stage has been investigated, with the induced air flotation (IAF) in focus. The following parameters were considered concerning the IAF efficiency to remove detrimental substances: concentration of cationic foaming agent, pH value, calcium concentration, and temperature. The amounts and characteristics of residual DCS were determined by gas chromatography and turbidity measurements. Residual concentrations of the foaming agent dodecyltrimetylammonium chloride were determined by electrospray ionization mass spectrometry. Up to 90% of pitch was removed, whereas hemicelluloses, which are important in preventing pitch problems, remained in the waters. Up to 70% of the pectic acids accounted for the high cationic demand of the process waters were removed by optimization of the IAF parameters. The presented separation process gives new opportunities to a selective purification of the process waters.

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.

In this investigation a new type of recoverable complexing agent (chelating surfactant) has been compared with a conventional complexing agent; diethylenetriamine pentaacetic acid (DTPA), in the metal ion sequestering of thermomechanical pulps (TMP) to be hydrogen peroxide bleached. After different degrees of washing of the pulps, bleaching experiments at different total alkali charges were performed with and without sodium silicate additions, and the ISO brightness of hand-made sheets was measured. The residual hydrogen peroxide in the bleaching liquor was also determined. No significant difference in either the brightness development or the residual hydrogen peroxide content could be detected between the pulps treated with equivalent molar ratios of the different complexing agents. Furthermore, the recovery of the chelating surfactant-manganese complexes from laboratory made white water by froth flotation was also studied. Two different foaming agents; sodium dodecyl sulphonate (SDS) and dimethyldodecylamine oxide (DDAO), were tested in the froth generation. After an addition of 160 ppm of DDAO, more than 80% of the manganese chelates could be recovered in the foam, containing 3% of the initial water mass.

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.

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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.

The influence of a chelating surfactant, different foaming agents, cationic polyelectrolytes, pH value, and temperature on the purification efficiency of process waters from a mechanical pulp mill has been studied by flotation in a 1 L customized unit. Turbidity measurements and gas chromatography (GC) were carried out to determine the removal and characteristics of dissolved and colloidal substances (DisCo). The manganese ion content in the process waters before flotation and the metal chelate removal capacity by flotation were determined by Inductively Coupled Plasma (ICP) and Atomic Absorption Spectrometry (AAS) measurements. It was found that a 99% removal of complex bound manganese ions and a 94% decrease in turbidity of the TMP water produced at the laboratory can be achieved in a single-stage flotation with a chelating surfactant and a foaming agent. Furthermore, a 91% decrease in turbidity, the removal of up to 96% of resin and fatty acids, and 93% of triglycerides from TMP water can be obtained after application of a foaming agent.