Effect of anionic salts in concentrate mixture on some blood and urine minerals, acid-base balance and feed intake of dry pregnant cows on grass silage based feeding with high calcium intake

Selostus: Kationi-anionitasapaino ummessaolevien lypsylehmien säilörehuruokinnassa kalsiumin saannin ollessa runsas

Effect of anionic salts in concentrate mixture and calcium intake on some blood and urine minerals, acid-base balance and feed intake of dry pregnant cows on grass silage based feeding

Selostus: Kationi-anionitasapaino ja kalsiumin saanti ummessaolevien lypsylehmien säilörehuruokinnassa

Effect of anionic salts in concentrate mixture and magnesium intake on some blood and urine minerals and acid-base balance of dry pregnant cows on grass silage based feeding

Selostus: Kationi-anionitasapaino ja magnesiumin saanti ummessaolevien lypsylehmien säilörehuruokinnassa

Effect of anionic salts on some blood and urine minerals, acid-base balance and udder oedema of dry pregnant cows

Selostus: Anionisten suolojen vaikutus ummessa olevien lehmien veren ja virtsan kivennäisiin, happo-emästasapainoon sekä utarepöhöön

Application of cerium oxide thin films grown by atomic layer deposition for soot removal

The objective of the thesis is to study cerium oxide thin films grown by the atomic layer deposition (ALD) for soot removal. Cerium oxide is one of the most important heterogeneous catalysts and can be used in particulate filters and sensors in a diesel exhaust pipe. Its redox/oxidation properties are a key factor in soot oxidation. Thus, the cerium oxide coating can help to keep particulate filters and sensors clean permanently. The literature part of the thesis focuses on the soot removal, introducing the origin and structure of soot, reviewing emissions standards for diesel particulate matter, and presenting methods and catalysts for soot removal. In the experimental part the optimal ALD conditions for cerium oxide were found, the structural properties of cerium oxide thin films were analyzed, and the catalytic activity of the cerium oxide for soot oxidation was investigated. Studying ALD growth conditions of cerium oxide films and determining their critical thickness range are important to maximize the catalytic performance operating at comparatively low temperature. It was found that the cerium oxide film deposited at 300 °C with 2000 ALD cycles had the highest catalytic activity. Although the activity was still moderate and did not decrease the soot oxidation temperature enough for a real-life application. The cerium oxide thin film deposited at 300 °C has a different crystal structure, surface morphology and elemental composition with a higher Ce3+ concentration compared to the films deposited at lower temperatures. The different properties of the cerium oxide thin film deposited at 300 °C increase the catalytic activity most likely due to higher surface area and addition of the oxygen vacancies.

Purification and fractionation by nanotiltration in dairy and sugar and sweetener industry applications

Nanotiltration is a membrane separation method known for its special characteristic of rejecting multivalent ions and passing monovalent ions. Thus, it is commonly applied with dilute aqueous solutions in partial salt removal, like in drinking water production. The possibilities of nanofiltration have been studied and the technique applied in a wide branch of industries, e.g. the pulp and paper, the textile and the chemical processing industry. However, most present applications and most of the potential applications studied involve dilute solutions, the permeating stream being generally water containing monovalent salts. In this study nanotiltration is investigated more as a fractionation method. A well-known application in the dairy industry is concentration and partial salt removal from whey. Concentration and partial demineralization is beneficial for futher processing of whey as whey concentrates are used e.g. in baby foods. In the experiments of this study nanotiltration effectively reduced the monovalent salts in the whey concentrate. The main concern in this application is lactose leakage into the permeate. With the nanofiltration membranes used the lactose retentions were practically ? 99%. Another dairy application studied was the purification and reuse of cleaning solutions. This is an environmentally driven application. An 80% COD reduction by nanofiltration was observed for alkaline cleaning-in-place solution. Nanofiltration is not as commonly applied in the sugar and sweeteners industry as in the dairy industry. In this study one potential application was investigated, namely xylose purification from hemicellulose hydrolyzate. Xylose is raw material for xylitol production. Xylose separation from glucose was initially studied with xylose-glucose model solutions. The ability of nanofiltration to partially separate xylose into the permeate from rather concentrated xylose-glucose solutions (10 w-% and 30 w-%) became evident. The difference in size between xylose and glucose molecules according to any size measure is small, e.g. the Stokes diameter of glucose is 0.73 nm compared to 0.65 nm for xylose. In further experiments, xylose was purified into nanoliltration permeate from a hemicellulose hydrolyzate solution. The xylose content in the total solids was increased by 1.4—1.7 fold depending on temperature, pressure and feed composition.

Effect of physico-chemical conditions and operating parameters on flux and retention of different components in ultrafiltration and nanofiltration fractionation of sweet whey

Tässä väitöstutkimuksessa tutkittiin fysikaaliskemiallisten olosuhteiden ja toimintaparametrien vaikutusta juustoheran fraktiointiin. Kirjallisuusosassa on käsitelty heran ympäristövaikutusta, heran hyödyntämistä ja heran käsittelyä kalvotekniikalla. Kokeellinen osa on jaettu kahteen osaan, joista ensimmäinen käsittelee ultrasuodatusta ja toinen nanosuodatusta juustoheran fraktioinnissa. Ultrasuodatuskalvon valinta tehtiin perustuen kalvon cut-off lukuun, joka oli määritetty polyetyleeniglykoliliuoksilla olosuhteissa, joissa konsentraatiopolariosaatioei häiritse mittausta. Kriittisen vuon konseptia käytettiin sopivan proteiinikonsentraation löytämiseksi ultrasuodatuskokeisiin, koska heraproteiinit ovat tunnetusti kalvoa likaavia aineita. Ultrasuodatuskokeissa tutkittiin heran eri komponenttien suodattumista kalvon läpi ja siihen vaikuttavia ominaisuuksia. Herapermeaattien peptidifraktiot analysoitiin kokoekskluusiokromatografialla ja MALDI-TOF massaspektrometrillä. Kokeissa käytettävien nanosuodatuskalvojen keskimääräinen huokoskoko analysoitiin neutraaleilla liukoisilla aineilla ja zeta-potentiaalit virtauspotentiaalimittauksilla. Aminohappoja käytettiin malliaineina tutkittaessa huokoskoon ja varauksen merkitystä erotuksessa. Aminohappojen retentioon vaikuttivat pH ja liuoksen ionivahvuus sekä molekyylien väliset vuorovaikutukset. Heran ultrasuodatuksessa tuotettu permeaatti, joka sisälsi pieniä peptidejä, laktoosia ja suoloja, nanosuodatettiin happamassa ja emäksisessä pH:ssa. Emäksisissä oloissa tehdyssä nanosuodatuksessa foulaantumista tapahtui vähemmän ja permeaattivuo oli parempi. Emäksisissä oloissa myös selektiivisyys laktoosin erotuksessa peptideistä oli parempi verrattuna selektiivisyyteen happamissa oloissa.

Kalvojen vertailu heran nanosuodatuksessa

Työssä verrattiin kaupallisia nanosuodatuskalvoja heran konsentroinnissa. Tutkitut kalvot olivat Desal-5 DK, NF45 ja Koch SR1. NF45-kalvosta tutkittiin kahta eri sukupolven kalvoa. Konsentrointiajoja tehtiin sekä laboratoriomittakaavan levysuotimella että pilot-mittakaavan spiraalimoduulilaitteella. Lisäksi tutkittiin juoksute- ja happoheran konsentrointien eroja. Erityistä huomiota kiinnitettiin permeaattivuon arvoihin konsentroinnissa ja kalvojen suolojen ja laktoosin pidätyskykyyn. NF45-kalvon uuden sukupolven malli osoittautui mittauksissa samankaltaiseksi suolojen ja laktoosin pidätyskyvyltään kuin Desal-5 DK. Koch SR1-kalvo, jonka suolojen ja laktoosin pidätyskyky on Desal-5 DK-kalvoa heikompi, puolestaan vastaa ominaisuuksiltaan NF45 vanhan sukupolven kalvoa. Vanhan sukupolven NF45-kalvon valmistus on loppunut keväällä 2000. Vaihdettaessa vanhan sukupolven NF45-kalvot uuden sukupolven kalvoihin on odotettavissa pienemmät permeaattivuot ja suuremmat suolojen ja laktoosin retentiot kuin aiemmin NF45-kalvolla. Juoksuteheran konsentroinnissa suurimmat permeaattivuot saatiin Koch SR1-kalvolla. Levysuotimella ja spiraalimoduulilla saadaan koostumukseltaan samanlainen juoksuteheratiiviste. Levysuotimella permeaattivuot ovat samalla konsentrointikertoimella suuremmat kuin spiraalimoduulilla. Tämä johtuu spiraalimoduuliin jäävistä kuolleista alueista, joissa ei ole virtausta. Uutta prosessia suunniteltaessa voidaan käyttää laboratoriomittakaavan levysuodinkokokeita, kun halutaan tietoa saatavan tuotteen koostumuksesta. Prosessin tuotantokapasiteetin arvioimiseen tarvitaan pilot-mittakaavan spiraalimoduulikokeita. Happoheratiiviste sisältää enemmän suoloja kuin samalla kalvolla valmistettu juoksuteheratiiviste. Tämä johtuu happoheran juoksuteheraa suuremmasta suolapitoisuudesta. Lisäksi happoheran konsentroinnin permeaattivuo on pienempi kuin juoksuteheran permeaattivuo, sillä happoheran alhainen pH, noin 4,5, vaikuttaa kalvon permeabiliteettiin heikentävästi.

Stabilization of the ionic form of weak acid cation exchange resins

Weak acid cation exchange (WAC) resins are used in the chromatographic separation of betaine from vinasse, a by-product of sugar industry. The ionic form of the resin determines the elution time of betaine. When a WAC-resin is in hydrogen form, the retention time of betaine is the longest and betaine elutes as the last component of vi-nasse from the chromatographic column. If the feed solution contains salts and its pH is not acidic enough to keep the resin undissociated, the ionic form of the hydrogen form resin starts to alter. Vinasse contains salts and its pH is around 5, it also contains weak acids. To keep the metal ion content (Na/H ratio) of the resin low enough to ensure successful separation of betaine, acid has to be added to either eluent (water) or vinasse. The aim of the present work was to examine by laboratory experiments which option requires less acid. Also the retention mechanism of betaine was investigated by measuring retention volumes of acetic acid and choline in different Na/H ratios of the resin. It was found that the resulting ionic form of the resin is the same regardless of whether the regeneration acid is added to the eluent or the feed solution (vinasse). Be-sides the salt concentration and the pH of vinasse, also the concentration of weak acids in the feed affects the resulting ionic form of the resin. The more buffering capacity vinasse has, the more acid is required to keep the ionic form of the resin desired. Vinasse was found to be quite strong buffer solution, which means relatively high amounts of acid are required to prevent the Na/H ratio from increasing too much. It is known that the retention volume of betaine decreases significantly, when the Na/H ratio increases. This is assumed to occur, because the amount of hydrogen bonds between the carboxylic groups of betaine and the resin decreases. Same behavior was not found with acetic acid. Choline has the same molecular structure as betaine, but instead of carboxylic group it has hydroxide group. The retention volume of choline increased as the Na/H ratio of the resin increased, because of the ion exchange reaction between choline cation and dissociated carboxylic group of the resin. Since the retention behavior of choline on the resin is opposite to the behavior of be-taine, the strong affinity of betaine towards hydrogen form WAC-resin has to be based on its carboxylic group. It is probable that the quaternary ammonium groups also affect the behavior of the carboxylic groups of betaine, causing them to form hydrogen bonds with the carboxylic groups of the resin.

Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Paineviemärissä muodostuvan rikkivedyn vähentäminen kemikaloimalla

Anaerobisissa olosuhteissa muodostuva rikkivetykaasu on tyypillinen ongelma etenkin pitkillä paineviemäriosuuksilla. Sille ominainen epämiellyttävä haju aiheuttaa jätevedenkäsittelyverkostoissa ja viemärilinjojen lähialueilla merkittäviä hajuongelmia. Lisäksi rikkivedyn hapettuessa rikkihapoksi viemäri joutuu alttiiksi korroosiolle. Helsingin Etelä rannassa sijaitsevaan Munkkisaareen päätyy 4,4 km pitkä paineviemäri. Viemärin tuuletusputken kautta leviävä rikkivety on aiheuttanut hajuongelmia alueella. Korkeimmat mitatut rikkivetypitoisuudet tuuletusputken läheisyydessä olivat jopa 300 ppm. Tutkimuksessa tehtiin koeajoja erilaisilla hajunpoistokemikaaleilla rikkivetyongelman ratkaisemiseksi. Viemäriin annosteltiin sen alkupäässä jatkuvatoimisesti ferrosulfaattia ja ferrinitraattisulfaattia, sekä shokki-käsittelyllä natriumhydroksidia (lipeää). Munkkisaaressa mitatut rikkivetypitoisuudet osoittivat käytettyjen kemikaalien tehokkuuden rikkivedyn poistossa. Rikkivedyn saostamiseen tarkoitetut rautasuolat (ferrosulfaatti ja ferrinitraattisulfaatti) vähensivät 100 - 150 g annoksilla rikkivetyä yli 90 prosenttia. Natriumhydroksin annoksella 3600 g/m³ viemärin mikrobiologinen toiminta voitiin estää keskimäärin kymmeneksi päiväksi, mutta tehokas rikkivedyn muodostumisen esto vaatisi käsittelyn uusimisen noin 5 päivän välein. Normaaleissa viemärin olosuhteissa rikkivetyä muodostui vuorokauden aikana yhtä neliömetriä kohden noin 10 g. Kemikaalikäsittelyjen avulla muodostuminen aleni parhaimmillaan kymmenesosaan alkuperäisestä. Tulosten perusteella kemikaalien käytöllä viemärissä voisi välttyä kalliilta saneeraukselta Munkkisaaressa sekä muissa korroosiolle alttiiksi joutuvissa viemäreissä. Kemikalointikustannukset rautasuoloilla olivat noin 11 000 - 34 000 € ja lipeällä noin 7 000 € vuodessa.

Treatment of oily wastewater by ultrafiltration: The effect of different operating and solution conditions

In many industries, such as petroleum production, and the petrochemical, metal, food and cosmetics industries, wastewaters containing an emulsion of oil in water are often produced. The emulsions consist of water (up to 90%), oils (mineral, animal, vegetable and synthetic), surfactants and other contaminates. In view of its toxic nature and its deleterious effects on the surrounding environment (soil, water) such wastewater needs to be treated before release into natural water ways. Membrane-based processes have successfully been applied in industrial applications and are considered as possible candidates for the treatment of oily wastewaters. Easy operation, lower cost, and in some cases, the ability to reduce contaminants below existing pollution limits are the main advantages of these systems. The main drawback of membranes is flux decline due tofouling and concentration polarisation. The complexity of oil-containing systems demands complementary studies on issues related to the mitigation of fouling and concentration polarisation in membranebased ultrafiltration. In this thesis the effect of different operating conditions (factors) on ultrafiltration of oily water is studied. Important factors are normally correlated and, therefore, their effect should be studied simultaneously. This work uses a novel approach to study different operating conditions, like pressure, flow velocity, and temperature, and solution properties, like oil concentration (cutting oil, diesel, kerosene), pH, and salt concentration (CaCl2 and NaCl)) in the ultrafiltration of oily water, simultaneously and in a systematic way using an experimental design approach. A hypothesis is developed to describe the interaction between the oil drops, salt and the membrane surface. The optimum conditions for ultrafiltration and the contribution of each factor in the ultrafiltration of oily water are evaluated. It is found that the effect on permeate flux of the various factors studied strongly depended on the type of oil, the type of membrane and the amount of salts. The thesis demonstrates that a system containing oil is very complex, and that fouling and flux decline can be observed even at very low pressures. This means that only the weak form of the critical flux exists for such systems. The cleaning of the fouled membranes and the influence of different parameters (flow velocity, temperature, time, pressure, and chemical concentration (SDS, NaOH)) were evaluated in this study. It was observed that fouling, and consequently cleaning, behaved differently for the studied membranes. Of the membranes studied, the membrane with the lowest propensity for fouling and the most easily cleaned was the regenerated cellulose membrane (C100H). In order to get more information about the interaction between the membrane and the components of the emulsion, a streaming potential study was performed on the membrane. The experiments were carried out at different pH and oil concentration. It was seen that oily water changed the surface charge of the membrane significantly. The surface charge and the streaming potential during different stages of filtration were measured and analysed being a new method for fouling of oil in this thesis. The surface charge varied in different stages of filtration. It was found that the surface charge of a cleaned membrane was not the same as initially; however, the permeability was equal to that of a virgin membrane. The effect of filtration mode was studied by performing the filtration in both cross-flow and deadend mode. The effect of salt on performance was considered in both studies. It was found that salt decreased the permeate flux even at low concentration. To test the effect of hydrophilicity change, the commercial membranes used in this thesis were modified by grafting (PNIPAAm) on their surfaces. A new technique (corona treatment) was used for this modification. The effect of modification on permeate flux and retention was evaluated. The modified membranes changed their pore size around 33oC resulting in different retention and permeability. The obtained results in this thesis can be applied to optimise the operation of a membrane plant under normal or shock conditions or to modify the process such that it becomes more efficient or effective.

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.

Modeling of electrolyte sorption – from phase equilibria to dynamic separation systems

In this thesis, general approach is devised to model electrolyte sorption from aqueous solutions on solid materials. Electrolyte sorption is often considered as unwanted phenomenon in ion exchange and its potential as an independent separation method has not been fully explored. The solid sorbents studied here are porous and non-porous organic or inorganic materials with or without specific functional groups attached on the solid matrix. Accordingly, the sorption mechanisms include physical adsorption, chemisorption on the functional groups and partition restricted by electrostatic or steric factors. The model is tested in four Cases Studies dealing with chelating adsorption of transition metal mixtures, physical adsorption of metal and metalloid complexes from chloride solutions, size exclusion of electrolytes in nano-porous materials and electrolyte exclusion of electrolyte/non-electrolyte mixtures. The model parameters are estimated using experimental data from equilibrium and batch kinetic measurements, and they are used to simulate actual single-column fixed-bed separations. Phase equilibrium between the solution and solid phases is described using thermodynamic Gibbs-Donnan model and various adsorption models depending on the properties of the sorbent. The 3-dimensional thermodynamic approach is used for volume sorption in gel-type ion exchangers and in nano-porous adsorbents, and satisfactory correlation is obtained provided that both mixing and exclusion effects are adequately taken into account. 2-Dimensional surface adsorption models are successfully applied to physical adsorption of complex species and to chelating adsorption of transition metal salts. In the latter case, comparison is also made with complex formation models. Results of the mass transport studies show that uptake rates even in a competitive high-affinity system can be described by constant diffusion coefficients, when the adsorbent structure and the phase equilibrium conditions are adequately included in the model. Furthermore, a simplified solution based on the linear driving force approximation and the shrinking-core model is developed for very non-linear adsorption systems. In each Case Study, the actual separation is carried out batch-wise in fixed-beds and the experimental data are simulated/correlated using the parameters derived from equilibrium and kinetic data. Good agreement between the calculated and experimental break-through curves is usually obtained indicating that the proposed approach is useful in systems, which at first sight are very different. For example, the important improvement in copper separation from concentrated zinc sulfate solution at elevated temperatures can be correctly predicted by the model. In some cases, however, re-adjustment of model parameters is needed due to e.g. high solution viscosity.