Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Formation of polyelectrolyte multilayers and polyelectrolyte complexes in dual polymer treatment of papermaking pulp

The goal of this study was to find a new approach to modify chemically the properties of paper by improving fiber quality. This Master’s thesis includes the multiple polymer treatment in general and themeasurement methods with which the formation of multilayers and complexes can be noticed. The treatment by an oppositely charged dual polymer system is a good approach to increase paper strength. In this work, starch, a cationic polymer, and carboxymethyl cellulose (CMC), an anionic polymer, were used step-by-step to improve paper strength. The adsorption of cationic starch and CMC on cellulose fibers were analyzed via polyelectrolyte titration. The results showed that paper strength was enhanced slightly with a layer-by-layer assembly of the polymers. However, if the washing stage, which was required for layer-by-layer assembly, was eliminated, the starch/CMC complex was deposited on fibers more efficiently, and the paper strength was improved more significantly.

Bleached kraft pulp production from Pinus tecunumanii (Eguiluz e Perry)

The use of 12-year-old Pinus tecunumanii (Eguiluz e Perry) grown in Colombia was evaluated for bleached kraft pulp production. Kraft pulps of kappa number 30 ± 1 were produced, and oxygen delignified and bleached to 90% ISO with ECF processes. The bleached pulps produced under optimum conditions were evaluated with regard to their strength properties. Pinus tecunumanii wood required low effective alkali charge to reach the desired kappa number and the unbleached pulp showed high oxygen delignification efficiency and bleachability when a OD(EO)DED sequence was used. The bleached pulps presented good physical-mechanical properties, which are comparable to those obtained with more traditional pines such as Pinus taeda and Pinus radiata. The results demonstrate that this tropical pine species is a suitable raw material for bleached kraft pulp production

The effect of wood supply and bleaching process on pulp brightness stability

One hundred different 5.5-year-old Eucalyptus grandis x Eucalyptus urophylla wood clones were cooked to kappa number 15-17.5 and the resulting kraft pulps oxygen-delignified to kappa 9.5-11.5 under fixed conditions, except for chemical charges. Thirteen samples showing large variations in effective alkali requirement, pulp yield and O-stage efficiency and selectivity were selected for brightness reversion studies. These samples were bleached to 90-91% ISO by DEDD and DEDP sequences and their brightness stability and chemical characteristics determined. Heat reversion of the eucalyptus kraft pulps was strongly influenced by the wood supply, with brightness loss varying in the range of 2.1-3.6 and 0.8-1.7 %ISO for ODEDD and ODEDP bleached pulps, respectively. Pulps bleached by the ODEDP sequence showed reversion values 1.3-1.9 % ISO lower than those bleached by the ODEDD sequence. Pulp carbonyl content decreased by 35-40% during the final peroxide bleaching stage. Carbonyl and carboxyl groups correlated positively with brightness reversion, as did permanganate number and acid soluble lignin. Pulp final viscosity and metal and DCM extractives contents showed no significant correlation with brightness reversion. Pulping, oxygen delignification and ECF bleaching performances also showed no correlation with brightness reversion.

Energy Efficiency of Pumping Medium Consistency Pulp with Centrifugal Pump

Approximately a quarter of electrical power consumption in pulp and paper industry is used in different pumping systems. Therefore, improving pumping system efficiency is a considerable way to reduce energy consumption in different processes. Pumping of wood pulp in different consistencies is common in pulp and paper industry. Earlier, centrifugal pumps were used to pump pulp only at low consistencies, but development of MC technology has made it possible to pump medium consistency pulp. Pulp is a non-Newtonian fluid, which flow characteristics are significantly different than what of water. In this thesis is examined the energy efficiency of pumping medium consistency pulp with centrifugal pump. The factors effecting the pumping of MC pulp are presented and through case study is examined the energy efficiency of pumping in practice. With data obtained from the case study are evaluated the effects of pump rotational speed and pulp consistency on energy efficiency. Additionally, losses caused by control valve and validity of affinity laws in pulp pumping are evaluated. The results of this study can be used for demonstrating the energy consumption of MC pumping processes and finding ways to improve energy efficiency in these processes.

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.

Microencapsulation of pequi pulp by spray drying: use of modified starches as encapsulating agent

The aim of this study was to evaluate the microencapsulation of pequi pulp by spray drying. A central composite rotational design was used in order to evaluate the effect of the independent variables: inlet air temperature, surfactant concentration and modified starch concentration. The dependent variables were assumed as yield of the process and the product features microencapsulated. A selection of the best process condition was performed to obtain the best condition of a product with the highest vitamin C and carotenoids content. Powders showed moisture content below 2%. The experimental values of hygroscopicity, yield, water activity, total carotenoids and vitamin C powders ranged from 7.96 to 10.67 g of adsorbed water/100g of solids, 24.34 to 49.80%, 0.13 to 0.30, 145.78 to 292.11 mg of ascorbic acid/g of pequi solids and 15.51 to 123.42 mg of carotenoids/g of pequi solids, respectively. The inlet air temperature 140°C, the surfactant concentration of 2.5% and the modified starch concentration of 22.5% was recommended as the selected condition. By the scanning electron microscopy, it was observed that most of the particles had spherical shape and smooth surface.

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.

Sorption of metal ions to wood, pulp and bark materials

Ett huvudmål med denna avhandling var att erhålla ny information om växelverkan mellan metalljoner i vattenfas och träbaserade material såsom olika pappersmassor, ved och bark. Material av gran, tall och björk har studerats. En ny känslig kolonnkromatografisk metod utvecklades för bestämning av affinitetsordningar för 17 olika metalljoner. Av dessa bands trevärt järn och de mycket toxiska tungmetallerna bly, koppar och kadmium starkast till de studerade materialen. Växelverkan i dessa tvåfas system sker som jonbyte, huvudsakligen via komplexbildning av metalljoner till funktionella grupper i den fasta fasen. Vattenfasens pH är den viktigaste parametern som bestämmer totala halten av metalljoner som binds till materialen. Resultatet i denna avhandling kan delvis betraktas som grundforskning. En ny kunskap om metalljoners förekomst och kemiska reaktioner i dessa system är även av stor ekonomisk och ekologisk, betydelse, när man strävar till allt mera slutna system i moderna massafabriker. Avhandlingen visar också att trädbark har stor potential för biosorption av tungmetaller t.ex. från avfallsvatten. Trädbark har nästan lika stor bindningskapacitet som dyra syntetiska jonbytare.

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.

The effect of timing temporary cements to treat induced pulp necrosis in the teeth of dogs

During endodontic therapy (pulpectomy, root canal debridement and root canal filling) microbiological management is a major concern. Bacteria present in dentine tubules, apical foramina and apical delta are causally related to failure of the procedure. Studies have shown that during single session endodontic treatment bacteria remain within dental structures. The aim of the present study was to evaluate endodontic treatment performed as two sessions, using temporary endodontic dressing materials for different periods in four groups of experimental dogs. A total of 80 roots of second and third upper premolar teeth and second, third and fourth lower premolar teeth were divided into four groups. The pulp chamber was opened with burrs and the pulp exposed for 60 days to induce pulpal inflammation and necrosis. Groups II, III and IV were treated with calcium hydroxide plus camphorated paramono-chlorophenol (PMCC) for 7, 15 and 30 days, respectively. In all groups, the root canals were filled with zinc oxide-eugenol and gutta-percha cones. Clinical and radiographical measurements were performed every 2 weeks. After 60 days a small block section containing the teeth, surrounding periapical tissues and the periodontium was removed for histological and microbiological study. Histological analysis revealed intense inflammatory response in all groups. Microbiological analysis showed microbial reduction inversely proportional to the period of time that the intracanal temporary medicament was left in place.

Characterization of fiber and vessel elements in pulp suspension images

The thesis is related to the topic of image-based characterization of fibers in pulp suspension during the papermaking process. Papermaking industry is focusing on process control optimization and automatization, which makes it possible to manufacture highquality products in a resource-efficient way. Being a part of the process control, pulp suspension analysis allows to predict and modify properties of the end product. This work is a part of the tree species identification task and focuses on analysis of fiber parameters in the pulp suspension at the wet stage of paper production. The existing machine vision methods for pulp characterization were investigated, and a method exploiting direction sensitive filtering, non-maximum suppression, hysteresis thresholding, tensor voting, and curve extraction from tensor maps was developed. Application of the method to the microscopic grayscale pulp images made it possible to detect curves corresponding to fibers in the pulp image and to compute their morphological characteristics. Performance of the method was evaluated based on the manually produced ground truth data. An accuracy of fiber characteristics estimation, including length, width, and curvature, for the acacia pulp images was found to be 84, 85, and 60% correspondingly.

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.