Ultrafine grinding of FGD and phosphogypsum with an attrition bead mill and a jet mill : optimisation and modelling of grinding and mill comparison

Fine powders of minerals are used commonly in the paper and paint industry, and for ceramics. Research for utilizing of different waste materials in these applications is environmentally important. In this work, the ultrafine grinding of two waste gypsum materials, namely FGD (Flue Gas Desulphurisation) gypsum and phosphogypsum from a phosphoric acid plant, with the attrition bead mill and with the jet mill has been studied. The ' objective of this research was to test the suitability of the attrition bead mill and of the jet mill to produce gypsum powders with a particle size of a few microns. The grinding conditions were optimised by studying the influences of different operational grinding parameters on the grinding rate and on the energy consumption of the process in order to achieve a product fineness such as that required in the paper industry with as low energy consumption as possible. Based on experimental results, the most influential parameters in the attrition grinding were found to be the bead size, the stirrer type, and the stirring speed. The best conditions, based on the product fineness and specific energy consumption of grinding, for the attrition grinding process is to grind the material with small grinding beads and a high rotational speed of the stirrer. Also, by using some suitable grinding additive, a finer product is achieved with a lower energy consumption. In jet mill grinding the most influential parameters were the feed rate, the volumetric flow rate of the grinding air, and the height of the internal classification tube. The optimised condition for the jet is to grind with a small feed rate and with a large rate of volumetric flow rate of grinding air when the inside tube is low. The finer product with a larger rate of production was achieved with the attrition bead mill than with the jet mill, thus the attrition grinding is better for the ultrafine grinding of gypsum than the jet grinding. Finally the suitability of the population balance model for simulation of grinding processes has been studied with different S , B , and C functions. A new S function for the modelling of an attrition mill and a new C function for the modelling of a jet mill were developed. The suitability of the selected models with the developed grinding functions was tested by curve fitting the particle size distributions of the grinding products and then comparing the fitted size distributions to the measured particle sizes. According to the simulation results, the models are suitable for the estimation and simulation of the studied grinding processes.

Fouling management and retention in nanofiltration of integrated paper mill effluents

Nanofiltration performance was studied with effluents from the pulp and paper industry and with model substances. The effect of filtration conditions and membrane properties on nanofiltration flux, retention, and fouling was investigated. Generally, the aim was to determine the parameters that influence nanofiltration efficiency and study how to carry out nanofiltration without fouling by controlling these parameters. The retentions of the nanofiltration membranes studied were considerably higher than those of tight ultrafiltration membranes, and the permeate fluxes obtained were approximately the same as those of tight ultrafiltration membranes. Generally, about 80% retentions of total carbon and conductivity were obtained during the nanofiltration experiments. Depending on the membrane and the filtration conditions, the retentions of monovalent ions (chloride) were between 80 and 95% in the nanofiltrations. An increase in pH improved retentions considerably and also the flux to some degree. An increase in pressure improved retention, whereas an increase in temperature decreased retention if the membrane retained the solute by the solution diffusion mechanism. In this study, more open membranes fouled more than tighter membranes due to higher concentration polarization and plugging of the membrane material. More irreversible fouling was measured for hydrophobic membranes. Electrostatic repulsion between the membrane and the components in the solution reduced fouling but did not completely prevent it with the hydrophobic membranes. Nanofiltration could be carried out without fouling, at least with the laboratory scale apparatus used here when the flux was below the critical flux. Model substances had a strong form of the critical flux, but the effluents had only a weak form of the critical flux. With the effluents, some fouling always occurred immediately when the filtration was started. However, if the flux was below the critical flux, further fouling was not observed. The flow velocity and pH were probably the most important parameters, along with the membrane properties, that influenced the critical flux. Precleaning of the membranes had only a small effect on the critical flux and retentions, but it improved the permeability of the membranes significantly.

Optimization of energy in a pulp mill

This study presents examination of ways to increase power generation in pulp mills. The main purpose was to identify and verify the best ways of power generation growth. The literature part of this study presented operation of energy pulp mill departments, energy consumption and generation by the recovery and power boilers. The second chapter of this part described the main directions for increase of electricity generation rise of black liquor dry solid content, increase of main steam parameters, flue gas heat recovery technologies, feed water and combustion air preheating. The third chapter of the literature part presented possible technical, environment and corrosion risks appeared from described alternatives. In the experimental part of this study, calculations and results of possible models with alternatives was presented. The possible combinations of alternatives were generated in 44 `models of energy pulp mill. The target of this part was define extra electricity generation after alternatives using and estimate profitability of generated models. The calculations were made by computer programme PROSIM. In the conclusions, the results were estimated on the basis of extra electricity generation and equipment design data of models. The profitability of cases was verified by their payback periods and additional incomes.

Effect of forest-based biofuels production on carbon footprint, Case: Integrated LWC paper mill

International energy and climate strategies also set Finland’s commitments to increasing the use of renewable energy sources and reducing greenhouse gas emissions. The target can be achieved by, for example, increasing the use of energy wood. Finland’s forest biomass potential is significant compared with current use. Increased use will change forest management and wood harvesting methods however. The thesis examined the potential for integrated pulp and paper mills to increase bioenergy production. The effects of two bioenergy production technologies on the carbon footprint of an integrated LWC mill were studied at mill level and from the cradle-to-customer approach. The LignoBoost process and FT diesel production were chosen as bioenergy cases. The data for the LignoBoost process were obtained from Metso and for the FT diesel process from Neste Oil. The rest of the information is based on the literature and databases of the KCL-ECO life-cycle computer program and Ecoinvent. In both case studies, the carbon footprint was reduced. From the results, it can be concluded that it is possible to achieve a fossil-fuel-free pulp mill with the LignoBoost process. By using steam from the FT diesel process, the amount of auxiliary fuel can be reduced considerably and the bark boiler can be replaced. With a choice of auxiliary fuels for use in heat production in the paper mill and the production methods for purchased electricity, it is possible to affect the carbon footprints even more in both cases.

Identification of extractives and polysaccharides as foulants in membrane filtration of pulp and paper mill effluents

The search for new renewable materials has intensified in recent years. Pulp and paper mill process streams contain a number of potential compounds which could be used in biofuel production and as raw materials in the chemical, food and pharmaceutical industries. Prior to utilization, these compounds require separation from other compounds present in the process stream. One feasible separation technique is membrane filtration but to some extent, fouling still limits its implementation in pulp and paper mill applications. To mitigate fouling and its effects, foulants and their fouling mechanisms need to be well understood. This thesis evaluates fouling in filtration of pulp and paper mill process streams by means of polysaccharide model substance filtrations and by development of a procedure to analyze and identify potential foulants, i.e. wood extractives and carbohydrates, from fouled membranes. The model solution filtration results demonstrate that each polysaccharide has its own fouling mechanism, which also depends on the membrane characteristics. Polysaccharides may foul the membranes by adsorption and/or by gel/cake layer formation on the membrane surface. Moreover, the polysaccharides interact, which makes fouling evaluation of certain compound groups very challenging. Novel methods to identify wood extractive and polysaccharide foulants are developed in this thesis. The results show that it is possible to extract and identify wood extractives from membranes fouled in filtration of pulp and paper millstreams. The most effective solvent was found to be acetone:water (9:1 v/v) because it extracted both lipophilic extractives and lignans at high amounts from the fouled membranes and it was also non-destructive for the membrane materials. One hour of extraction was enough to extract wood extractives at high amounts for membrane samples with an area of 0.008 m2. If only qualitative knowledge of wood extractives is needed a simplified extraction procedure can be used. Adsorption was the main fouling mechanism in extractives-induced fouling and dissolved fatty and resin acids were mostly the reason for the fouling; colloidal fouling was negligible. Both process water and membrane characteristics affected extractives-induced fouling. In general, the more hydrophilic regenerated cellulose (RC) membrane fouled less that the more hydrophobic polyethersulfone (PES) and polyamide (PA) membranes independent of the process water used. Monosaccharide and uronic acid units could also be identified from the fouled synthetic polymeric membranes. It was impossible to analyze all monosaccharide units from the RC membrane because the analysis result obtained contained degraded membrane material. One of the fouling mechanisms of carbohydrates was adsorption. Carbohydrates were not potential adsorptive foulants to the sameextent as wood extractives because their amount in the fouled membranes was found to be significantly lower than the amount of wood extractives.

Stochastic variability of output levels in a pulp mill

Quite often, in the construction of a pulp mill involves establishing the size of tanks which will accommodate the material from the various processes in which case estimating the right tank size a priori would be vital. Hence, simulation of the whole production process would be worthwhile. Therefore, there is need to develop mathematical models that would mimic the behavior of the output from the various production units of the pulp mill to work as simulators. Markov chain models, Autoregressive moving average (ARMA) model, Mean reversion models with ensemble interaction together with Markov regime switching models are proposed for that purpose.

Ultrafiltration of pulp mill bleaching effluents

Main objective of this research was to find suitable polymeric ultrafiltration membranes with high retentions, good capacities and low fouling tendencies for the E2- and EP-effluent ultrafiltration. Purpose was to treat alkaline bleaching effluents with ultrafiltration in a way that permeates of the filtrations could be recycled back to process and the consumption of fresh water in the pulp mill could be reduced significantly. In the theoretical part of this work the challenges set by the pulp and paper indus-try processes for membranes were examined. An overview of the membrane tech-nology in the pulp industry was also provided. In addition process conditions in the chemical pulp bleaching and properties of bleaching effluents were discussed in literature study. In experimental part the E2- and EP-stage bleaching effluents from Stora Enso Imatra kraft pulp mill were ultrafiltered with CR250- and CR200-filters. Suitable membranes for ultrafiltration were chosen after screening experiments. Concentra-tion experiment was made for the E2-effluent in order to estimate water saving potential. The E2-effluent was finally ultrafiltered in the pulp mill in order to test the feasibility of ultrafiltration in a real industrial environment. Good membrane for the EP-effluent ultrafiltration based on the EP-screening ex-periments was polyethersulfone membrane UP020 with cut-off value of 20 000 Da. Polysulfone membrane UFX05 with cut-off value of 5 000 Da was promising membrane for the ultrafiltration of the E2-effluent. Based on the concentration filtration of the E2-effluent with UFX05 membrane the water saving potential could be 2.2 m3/Adt for the industrial scale ultrafiltration process. Retention re-sults, such as average COD retention of 60 %, from the trial filtration at the pulp mill with UFX05 membrane were modest compared to the screening experiments, where average COD retention was 75 %. Therefore tighter ultrafiltration mem-branes should be tested for the ultrafiltration of the E2-effluent. The UP020 mem-brane seemed to be suitable for the ultrafiltration of the EP-effluent however con-centration and pilot scale ultrafiltration experiments are needed to verify this.

Tal af John Stuart Mill

14 x 23 cm

Risk management measures for REACH registered intermediate substances in pulp mill

Tämän työn tavoitteena on antaa kuvaus riskinhallintamenetelmistä viidelle välituotekemikaalille, joita käytetään Stora Enson Imatran tehtailla. Välituotekemikaalit ovat mustalipeä, viherlipeä, valkolipeä, natriumbisulfiitti ja natriumsulfiitti. Nämä kemikaalit ovat jo rekisteröityjä ECHA:an ja rekisteröintiin liittyen ECHA:an on toimitettava myös kuvaus riskinhallintamenetelmistä. Työn alussa kuvaillaan työn kannalta olennaiset säädökset ja viranomaiset, jotka valvovat kemikaalien käyttöä ja valmistusta Euroopan Unionin alueella. Tämän jälkeen kerrotaan yleisesti välituotekemikaalien rekisteröintikriteereistä. Työn loppuosa käsittää kuvauksen riskinhallintamenetelmistä jokaiselle kemikaalille. Riskinhallintamenetelmät sisältävät eristyksen teknisin keinoin, menettelytapa- ja valvontatekniikat, johtamistavat ja henkilökunnan koulutuksen ja välituotekemikaalien kuljetuksen. Myös jokaisen kemikaalin ominaisuudet on kuvattu ja lyhyt prosessikuvaus kemikaalien valmistuksesta ja käytöstä on esitetty helpottamaan ymmärtämistä.

Electro-Oxidation Treatment of Pulp and Paper Mill Circulating Waters and Wastewaters

Interest in water treatment by electrochemical methods has grown in recent years. Electrochemical oxidation has been applied particularly successfully to degrade different organic pollutants and disinfect drinking water. This study summarizes the effectiveness of the electrochemical oxidation technique in inactivating different primary biofilm forming paper mill bacteria as well as sulphide and organic material in pulp and paper mill wastewater in laboratory scale batch experiments. Three different electrodes, borondoped diamond (BDD), mixed metal oxide (MMO) and PbO2, were employed as anodes. The impact on inactivation efficiency of parameters such as current density and initial pH or chloride concentration of synthetic paper machine water was studied. The electrochemical behaviour of the electrodes was investigated by cyclic voltammetry with MMO, BDD and PbO2 electrodes in synthetic paper mill water as also with MMO and stainless steel electrodes with biocides. Some suggestions on the formation of different oxidants and oxidation mechanisms were also presented during the treatment. Aerobic paper mill bacteria species (Deinococcus geothermalis, Pseudoxanthomonas taiwanensis and Meiothermus silvanus) were inactivated effectively (>2 log) at MMO electrodes by current density of 50 mA/cm2 and the time taken three minutes. Increasing current density and initial chloride concentration of paper mill water increased the inactivation rate of Deinococcus geothermalis. The inactivation order of different bacteria species was Meiothermus silvanus > Pseudoxanthomonas taiwanensis > Deinococcus geothermalis. It was observed that inactivation was mainly due to the electrochemically generated chlorine/hypochlorite from chloride present in the water and also residual disinfection by chlorine/hypochlorite occurred. In real paper mill effluent treatment sulphide oxidation was effective with all the different initial concentrations (almost 100% reduction, current density 42.9 mA/cm2) and also anaerobic bacteria inactivation was observed (almost 90% reduction by chloride concentration of 164 mg/L and current density of 42.9 mA/cm2 in five minutes). Organic material removal was not as effective when comparing with other tested techniques, probably due to the relatively low treatment times. Cyclic voltammograms in synthetic paper mill water with stainless steel electrode showed that H2O2 could be degraded to radicals during the cathodic runs. This emphasises strong potential of combined electrochemical treatment with this biocide in bacteria inactivation in paper mill environments.