Water vapor tightness of packages: methods and optimizing

Työn tarkoituksena oli testata jo tutkimuskeskuksella käytössä ollutta ja tutkimuskeskukselle tässä työssä kehitettyä pakkauksen vesihöyrytiiveyteen liittyvää mittausmenetelmää. Saatuja tuloksia verrattiin keskenään sekä materiaalista mitattuihin arvoihin. Elintarvikepakkauksia tutkittiin myös kosteussensoreiden, säilyvyyskokeen sekä kuljetussimuloinnin avulla. Optimoinnilla tutkittiin pakkauksen muodon vaikutusta vesihöyrytiiveyteen. Pakkauksen vesihöyrynläpäisyn mittaamiseen kehitetty menetelmä toimi hyvin ja sen toistettavuus oli hyvä. Verrattaessa sitä jo olemassa olleeseen menetelmään tulokseksi saatiin, että uusi menetelmä oli nopeampi ja vaati vähemmän työaikaa, mutta molemmat menetelmät antoivat hyviä arvoja rinnakkaisille näytteille. Kosteussensoreilla voitiin tutkia tyhjän pakkauksen sisällä olevan kosteuden muutoksia säilytyksen aikana. Säilyvyystesti tehtiin muroilla ja parhaan vesihöyrysuojan antoivat pakkaukset joissa oli alumiinilaminaatti- tai metalloitu OPP kerros. Kuljetustestauksen ensimmäisessä testissä pakkauksiin pakattiin muroja ja toisessa testissä nuudeleita. Kuljetussimuloinnilla ei ollutvaikutusta pakkausten sisäpintojen eheyteen eikä siten pakkausten vesihöyrytiiveyteen. Optimoinnilla vertailtiin eri muotoisten pakkausten tilavuus/pinta-ala suhdetta ja vesihöyrytiiveyden riippuvuutta pinta-alasta. Optimaalisimmaksi pakkaukseksi saatiin pallo, jonka pinta-ala oli pienin ja materiaalin sallima vesihöyrynläpäisy suurin ja vesihöyrybarrierin määrä pienin.

Factors affecting tightness of package

Työn tarkoituksena oli tutkia kartonkipohjaisten pakkausmateriaalien läpäisyominaisuuksia sekä pakkausten tiiveyteen vaikuttavia tekijöitä. Työssä verrattiin skaivatun ja skaivaamattoman raakareunan sekä tölkkien pohjaratkaisujen ominaisuuksia vesihöyryn- ja hapen läpäisevyydessä, kun käytetty kartonki oli molemmin puolin polymeeripäällystetty. Tiiveysominaisuuksia tutkittiin myös vuotomittauksin, värjäyksin ja elektronimikroskoopilla. Kuivan elintarvikkeen säilytystestillä ja kilpailijapakkausanalyyseillä oli tarkoituksena myös saada selville eri pakkausmateriaalien ja pakkauksien läpäisevyys- ja tiiveysominaisuuksia. Pakkauksen saumoilla oli yhtä suuri tai suurempi vaikutus vesihöyryn läpäisyssä kuin itse materiaalilla, kun pakkaus oli molemmin puolin polymeeripäällystetty kartonkikuppi. Skaivatun sauman vesihöyrynläpäisy oli vain 4-10 % pienempi kuin raakareunallisen sauman. Pakkauksen ulkopuolisten raakareunojen suojaaminen pienensi vesihöyrynläpäisevyyttä 30 %. Kun pakkauksen sisäpuolen raaka-reuna oli suojattu teipillä, saumoilla ei ollut niin suurta vaikutusta vesihöyryn läpäisyyn verrattuna materiaaliin. Raakareunan määrällä tölkin pohjassa tai pienillä vuodoilla tölkin saumoissa ei ollut merkitystä vesihöyryn läpäisyyn. Hapenläpäisyssä oli tärkeää ehyt barrierkerros. Polymeerisen barrierkerroksen reiät ja sauman skaivaus vaikuttivat enemmän kuin vesihöyryn läpäisyssä. Mitä enemmän tölkin pohjassa oli raakareunaa, sitä suurempi oli sen hapenläpäisy. Pakkauksen konvertointi, koneen säädöt ja lämmön kohdistus, ovat saattaneet aiheuttaa värjäyksellä havaitut barrierkerroksen mikroreiät. Kaupalliset kuiva-ainepakkaukset sisälsivät pääasiassa alumiinilaminaatin vesihöyryn, hapen ja valon suojana, kun tuotteena oli maitojauhetta ja rasvaa sisältävä elintarvike. Kuitenkin, jos pakkausmateriaali sisälsi vain ohuen sumutetun alumiinikerroksen, sen barrieriominaisuus ei ollut yhtä hyvä kuin alumiinilaminaatin. Äidinmaidonkorvikkeen säilytystestissä seurattiin eri analyysein tuotteen laatua kolmen kuukauden säilytyksen ajan. Pakkauksen vesihöyryn läpäisyominaisuus osoittautui tärkeimmäksi, sillä kosteuden vaikutus tuotteen laadun heikkenemisessä oli suurin. Hapen vaikutus on myös olennainen ja siten hyvä hapenestokerros sekä tiiveys ovat myös tärkeitä pakkauksen ominaisuuksia.

Nestepakkauskartongin kosteuden hallinta

Koska kartonki on hygroskooppista, sen kosteus on riippuvainen ilman lämpötilasta ja suhteellisesta kosteudesta. Liian korkea kosteus kartongissa aiheuttaa jäykkyyden alenemista, kartongin sitkeyttä, sekä pullistuneita pakkauksia kuluttajilla. Kosteusongelmia syntyy varastoinnissa, sekä kylmän rullan käsittelyn aikana lämpimissä tuotantotiloissa. Rullaa tulisi säilyttää tiiviissä paketissa, jotta se olisi suojattu ympäristön vaihtelevilta olosuhteilta. Jos pakkaus ei ole tiivis ja ympäröivä ilma pääsee kontaktiin kartongin kanssa kylmävarastoinnin aikana, nousee kartongin kosteus jo parissa vuorokaudessa yli 7 %:iin ilman lämpötilan ollessa 15 °C ja suhteellisen kosteuden 95 %. Kirjallisuusosan tavoitteena oli kartoittaa tekijät, joilla on vaikutusta kuitujen ominaisuuteen imeä itseensä kosteutta ympäröivästä ilmasta. Kokeellisessa osassa selvitettiin, oliko kartongin kosteuden nousu johtunut tasapainokosteuden nousemisesta. Painopisteenä oli tutkia kosteuden muutokset varastoinnin ja konvertoinnin sekä pakkaustuotteen käytön aikana. Simuloinnin avulla määritettiin kosteuden penetroituminen rullaan. Tutkittiin pakkausmateriaalien vesihöyrytiiveydet ja käärinnän vaikutus rullapakkauksen sisäisiin olosuhteisiin. Nestepakkauskartongin tasapainokosteus ei ollut muuttunut. Käytännön varastointikokeiden avulla havaittiin, että pinon päällimmäinen rulla altistui eniten ympäröivän ilman olosuhteiden muutoksille. Havaittiin myös kosteuseroa tämän rullan reunojen välillä. Mitä lyhyempi on varastointiaika kartongin päällystyksen jälkeen, sitä paremmin ehkäistään kosteuden noususta aiheutuvat haitat kartongissa. Maksimivarastointiaika rullille on 1,5 kuukautta, jolloin kartongin kosteus oli 6,5 % ja pinon päällimmäisessä rullassa noin 6,7 %. Pitkään varastoidusta kartongista valmistetuissa maitotölkeissä oli korkein kosteus, suurin pullistuma ja alhaisin otejäykkyys 10 päivän jälkeen täytöstä. Varastointiajan ollessa pitkä, kartongista tulee sitkeää ja venyvää, ja se sitoo enemmän kosteutta kuin mitä se on sitonut ennen varastoon tuloa. Skaivaus pienentää kosteuspenetraatiota raakakartonkiin, jolloin jäykkyys säilyy ja pullistuma pienenee pakkauksessa.

Model-based study of a chemical-looping combustion process

Chemical-looping combustion (CLC) is a novel combustion technology with inherent separation of the greenhouse gas CO2. The technique typically employs a dual fluidized bed system where a metal oxide is used as a solid oxygen carrier that transfers the oxygen from combustion air to the fuel. The oxygen carrier is looping between the air reactor, where it is oxidized by the air, and the fuel reactor, where it is reduced by the fuel. Hence, air is not mixed with the fuel, and outgoing CO2 does not become diluted by the nitrogen, which gives a possibility to collect the CO2 from the flue gases after the water vapor is condensed. CLC is being proposed as a promising and energy efficient carbon capture technology, since it can achieve both an increase in power station efficiency simultaneously with low energy penalty from the carbon capture. The outcome of a comprehensive literature study concerning the current status of CLC development is presented in this thesis. Also, a steady state model of the CLC process, based on the conservation equations of mass and energy, was developed. The model was used to determine the process conditions and to calculate the reactor dimensions of a 100 MWth CLC system with bunsenite (NiO) as oxygen carrier and methane (CH4) as fuel. This study has been made in Oxygen Carriers and Their Industrial Applications research project (2008 – 2011), funded by the Tekes – Functional Material program. I would like to acknowledge Tekes and participating companies for funding and all project partners for good and comfortable cooperation.

Influence of plasma modification on surface properties and offset printability of coated paper

The properties of the paper surface play a crucial role in ensuring suitable quality and runnability in various converting and finishing operations, such as printing. Plasma surface modification makes it possible to modify the surface chemistry of paper without altering the bulk material properties. This also makes it possible to investigate the role of the surface chemistry alone on printability without influencing the porous structure of the pigment-coated paper. Since the porous structure of a pigment coating controls both ink setting and optical properties, surface chemical changes created by a plasma modification have a potential to decouple these two effects and to permit a better optimization of them both. The aim of this work was to understand the effects of plasma surface modification on paper properties, and how it influences printability in the sheet-fed offset process. The objective was to broaden the fundamental understanding of the role of surface chemistry on offset printing. The effects of changing the hydrophilicity/ hydrophobicity and the surface chemical composition by plasma activation and plasma coatings on the properties of coated paper and on ink-paper interactions as well as on sheet-fed offset print quality were investigated. In addition, the durability of the plasma surface modification was studied. Nowadays, a typical sheet-fed offset press also contains units for surface finishing, for example UVvarnishing. The role of the surface chemistry on the UV-varnish absorption into highly permeable and porous pigment-coated paper was also investigated. With plasma activation it was possible to increase the surface energy and hydrophilicity of paper. Both polar and dispersion interactions were found to increase, although the change was greater in the polar interactions due to induced oxygen molecular groups. The results indicated that plasma activation takes place particularly in high molecular weight components such as the dispersion chemicals used to stabilize the pigment and latex particles. Surface composition, such as pigment and binder type, was found to influence the response to the plasma activation. The general trend was that pilot-scale treatment modified the surface chemistry without altering the physical coating structure, whereas excessive laboratory-scale treatment increased the surface roughness and reduced the surface strength, which led to micro-picking in printing. It was shown that pilot-scale plasma activation in combination with appropriate ink oils makes it possible to adjust the ink-setting rate. The ink-setting rate decreased with linseed-oil-based inks, probably due to increased acid-base interactions between the polar groups in the oil and the plasma-treated paper surface. With mineral-oil-based inks, the ink setting accelerated due to plasma activation. Hydrophobic plasma coatings were able to reduce or even prevent the absorption of dampening water into pigmentcoated paper, even when the dampening water was applied under the influence of nip pressure. A uniform hydrophobic plasma coating with sufficient chemical affinity with ink gave an improved print quality in terms of higher print density and lower print mottle. It was also shown that a fluorocarbon plasma coating reduced the free wetting of the UV-varnish into the highly permeable and porous pigment coating. However, when the UV-varnish was applied under the influence of nip pressure, which leads to forced wetting, the role of the surface chemical composition seems to be much less. A decay in surface energy and wettability occurred during the first weeks of storage after plasma activation, after which it leveled off. However, the oxygen/carbon elemental ratio did not decrease as a function of time, indicating that ageing could be caused by a re-orientation of polar groups or by a contamination of the surface. The plasma coatings appeared to be more stable when the hydrophobicity was higher, probably due to fewer interactions with oxygen and water vapor in the air.

Atomikerroskasvatuksen soveltaminen kemiantekniikassa

Tässä kirjallisuustyössä tutkittiin atomikerroskasvatuksen (ALD) soveltamista kemiantekniikassa. Työn alussa kerrottiin atomikerroskasvatuksesta, sen toimintaperiaatteista ja prosessitekniikasta. Tämän jälkeen tutkittiin viittä eri kemiantekniikan sovellusta, jotka olivat polymeerien pinnoittaminen, heterogeenisten katalyyttien syntetisointi, membraanien modifiointi, korroosionesto ja kaasunilmaisimet. ALD on ohutkalvotekniikka, jolla voidaan valmistaa nanometrin tai jopa Ångströmin (1 Å = 0.1 nm) tarkkuudella epäorgaanisia materiaalikerroksia, jotka yleensä ovat metallioksideja, kuten alumiinioksidi. ALD perustuu kaasu-kiintoainereaktioihin, joissa kaasumaiset kemialliset prekursorit reagoivat vuorotellen kasvualustan kanssa. Tyypilliset prekursorit ovat metalliligandi ja vesi, joka on yleisin hapen lähde ALD-reaktioissa. ALD−reaktiot suoritetaan yleensä matalassa paineessa (100−200 Pa) ja korkeassa lämpötilassa (200–400 °C) suljetussa reaktorikammiossa. ALD-prosesseissa voidaan hyödyntää myös plasmaa alentamaan reaktiolämpötiloja. Plasman avulla prekursoreista luodaan hyvin reaktiivisia radikaaleja, jotka voivat reagoida jopa huoneenlämmössä. Lämpöherkkiä polymeerejä voidaan pinnoittaa ohutkalvoilla, joilla voidaan lisätä esimerkiksi pakkausmateriaalien suojaa happea ja vesihöyryä vastaan. ALD:llä voidaan syntetisoida tarkasti nanomittakaavan heterogeenisiä katalyyttejä, joilla on korkea dispersio tukimateriaalin pinnalla. ALD:n avulla voidaan säästää katalyyttimateriaalia menettämättä katalyytin aktiivisuutta, mikä on tärkeää monien katalyyttisovellusten taloudellisuuden kannalta, esimerkiksi polttokennot. ALD soveltuu hyvin membraanien modifiointiin, koska kaasumaiset prekursorit leviävät tasaisesti membraanin huokosiin. Membraanien pinnoittamisella pyritään vaikuttamaan, selektiivisyyteen, hydrofiilisyyteen, liuotinkestävyyteen, huokoskokoon ja sen jakaumaan. Lisäksi membraaneja voidaan pinnoittaa katalyyttisillä ohutkalvoilla, mikä on tärkeää nanoreaktoreiden kehityksen kannalta. ALD:llä voidaan pinnoittaa esimerkiksi terästä, ja vähentää täten teräksen korroosiota. Puolijohtavia metallioksideja voidaan käyttää kaasunilmaisimina, joiden valmistuksessa ALD:n tarkkuudesta on suurta hyötyä.

Rasvankestävät paperit ja kartongit

Rasvankestävyydellä tarkoitetaan sitä, että materiaali hylkii tai kestää rasvaa tietyn ajan läpäisemättä sen pintaa. Rasvankestäviä papereita ja kartonkeja löytyy kaikkialta. Erilaiset ruuanvalmistuspaperit, kuten esimerkiksi leivinpaperi ja voipaperi, ovat rasvankestäviä. Myös pakkauksissa käytetään paljon rasvankestäviä papereita ja kartonkeja. Rasvankestäviltä tuotteilta vaaditaan erilaisia ominaisuuksia riippuen niiden käyttötarkoituksesta. Pakkausmateriaaleilta vaaditaan esimerkiksi lujuutta ja kestävyyttä fyysistä rasitusta, valoa, hajuja ja mikrobeja vastaan. Ruuanvalmistusmateriaaleilta vaaditaan puolestaan lujuutta ja kestävyyttä lämpöä, kosteutta ja fyysistä rasitusta vastaan. Rasvankestäviltä papereilta vaaditaan rasvankestävyyden lisäksi hyvää vetolujuutta, märkälujuutta ja hyviä optisia ominaisuuksia. Neliömassan tulee asettua 20─80 g/m2 välille ja metallipitoisuudet eivät saa olla liian korkeat. Myös tuotteiden kierrätettävyys on nostanut asemaansa viimeaikoina. Tuotteen tuotannon ja itse tuotteen ympäristöystävällisyys ovat todella arvostettuja kuluttajan, tuottajan, Suomen, EU:n ja koko maailman näkökulmista. Jotta tuotteesta saadaan rasvankestävää, vaaditaan siltä erilaisia barrier-ominaisuuksia. Rasvankestävällä paperilla vaaditaan hyviä barrier-ominaisuuksia esimerkiksi rasvan, ilman, veden, vesihöyryn sekä hapen läpäisevyyksissä. Rasvankestäviä papereita ja kartonkeja voidaan valmistaa kemiallisilla ja mekaanisilla tavoilla. Happokäsittely ja fluorokemikaalien lisääminen ovat kemiallisia tapoja, kun taas sellun jauhaminen pitkään matalassa lämpötilassa on mekaaninen tapa valmistaa rasvankestävää paperia. Näiden tapojen lisäksi rasvankestäviä papereita voidaan tehdä erilaisten pinnoitusten avulla. Erilaiset muovit ovat yleisemmin käytettyjä pinnoitemateriaaleja. Esimerkiksi PE- ja PET-päällysteet ovat käytettyjä rasvankestävissä tuotteissa. Viime aikoina on kehitetty paljon erilaisia biomateriaaleja, joista voidaan tehdä rasvankestävä pinnoite. Lipideistä, hydrokolloideista ja erilaisista komposiiteista voidaan luoda uusien tekniikoiden avulla rasvankestäviä pinnoitteita. Rasvankestävyydestä voidaan saada jonkinlainen käsitys WVTR-asteen, Cobb-arvon ja kontaktikulman mittausten avulla. Rasvankestävyyttä voidaan myös mitata erilaisten standarditestien avulla. TAPPI:lla, ISO:lla ja ASTM:llä on useita erilaisia standardeja. Lähes kaikissa rasvankestävyysstandardeissa tuloksen saaminen perustuu visuaaliseen havaintoon, mikä aiheuttaa välillä hankaluuksia tulosten luotettavuuteen, koska tuloksen määrittää ihmissilmä, ja kaikilla testin tekijöillä on erilainen silmä, joka aistii eri tavalla.

Possibility Of Controlling The Atmosphere Inside A Package Using Microperforation

This work focuses on the study of the determination on the possibilities of controlling the required moisture within the inside of film sealed packages. The task is based on the challenges faced by fresh food producers in actualizing a longer product shelf-life coupled with the growing complex desires coming from consumers in the aspect of quality. One way to realize this is by proper evaluation on the use of the flexible plastic films through permeation measurements on the required amount of moisture penetrating through the plastic film with the application of microperforation. A packaging material requires proper interaction on moisture transmission, between the product and the outside environment. The plastic film material that stands between, fresh fruits, vegetables and the outside environment could have appropriate respiration rates through possible micro holes. This work simulates similar process with the aid of water vapor transmission rate (WVTR) experiment using anhydrous CaCl2 as the desiccant, in studying the WVTR values of various perforated film materials at different conditions of storage (standard, fridge, and tropical conditions). However, the results showed absorption rates of water vapor at various conditions in grams of H2O/m2/24h.

Modification of commercial poly-lactide for extrusion coated food packaging applications

Poly-L-lactide (PLLA) is a widely used sustainable and biodegradable alternative to replace synthetic non-degradable plastic materials in the packaging industry. Conversely, its processing properties are not always optimal, e.g. insufficient melt strength at higher temperatures (necessary in extrusion coating processes). This thesis reports on research to improve properties of commercial PLLA grade (3051D from NatureWorks), to satisfy and extend end-use applications, such as food packaging by blending with modified PLLA. Adjustment of the processability by chain branching of commercial poly-L-lactide initiated by peroxide was evaluated. Several well-defined branched structures with four arms (sPLLA) were synthesized using pentaerythritol as a tetra-functional initiator. Finally, several block copolymers consisting of polyethylene glycol and PLLA (i.e. PEGLA) were produced to obtain a well extruded material with improved heat sealing properties. Reactive extrusion of poly-L-lactide was carried out in the presence of 0.1, 0.3 and 0.5 wt% of various peroxides [tert-butyl-peroxybenzoate (TBPB), 2,5-dimethyl-2,5-(tert-butylperoxy)-hexane (Lupersol 101; LOL1) and benzoyl peroxide (BPO)] at 190C. The peroxide-treated PLLAs showed increased complex viscosity and storage modulus at lower frequencies, indicating the formation of branched/cross linked architectures. The material property changes were dependent on the peroxide, and the used peroxide concentration. Gel fraction analysis showed that the peroxides, afforded different gel contents, and especially 0.5 wt% peroxide, produced both an extremely high molar mass, and a cross linked structure, not perhaps well suited for e.g. further use in a blending step. The thermal behavior was somewhat unexpected as the materials prepared with 0.5 wt% peroxide showed the highest ability for crystallization and cold crystallization, despite substantial cross linking. The peroxide-modified PLLA, i.e. PLLA melt extruded with 0.3 wt% of TBPB and LOL1 and 0.5 wt% BPO was added to linear PLLA in ratios of 5, 15 and 30 wt%. All blends showed increased zero shear viscosity, elastic nature (storage modulus) and shear sensitivity. All blends remained amorphous, though the ability of annealing was improved slightly. Extrusion coating on paperboard was conducted with PLLA, and peroxide-modified PLLA blends (90:10). All blends were processable, but only PLLA with 0.3 wt% of LOL1 afforded a smooth high quality surface with improved line speed. Adhesion levels between fiber and plastic, as well as heat seal performance were marginally reduced compared with pure 3051D. The water vapor transmission measurements (WVTR) of the blends containing LOL1 showed acceptable levels, only slightly lower than for comparable PLLA 3051D. A series of four-arm star-shaped poly-L-lactide (sPLLA) with different branch length was synthesized by ring opening polymerization (ROP) of L-lactide using pentaerythritol as initiator and stannous octoate as catalyst. The star-shaped polymers were further blended with its linear resin and studied for their melt flow and thermal properties. Blends containing 30 wt% of sPLLA with low molecular weight (30 wt%; Mwtotal: 2500 g mol-1 and 15000 g mol-1) showed lower zero shear viscosity and significantly increased shear thinning, while at the same time slightly increased crystallization of the blend. However, the amount of crystallization increased significantly with the higher molecular weight sPLLA, therefore the star-shaped structure may play a role as nucleating agent. PLLA-polyethylene glycol–PLLA triblock copolymers (PEGLA) with different PLLA block length were synthesized and their applicability as blends with linear PLLA (3051D NatureWorks) was investigated with the intention of improving heat-seal and adhesion properties of extrusion-coated paperboard. PLLA-PEG-PLLA was obtained by ring opening polymerization (ROP) of L-lactide using PEG (molecular weight 6000 g mol-1) as an initiator, and stannous octoate as catalyst. The structures of the PEGLAs were characterized by proton nuclear magnetic resonance spectroscopy (1H-NMR). The melt flow and thermal properties of all PEGLAs and their blends were evaluated using dynamic rheology, and differential scanning calorimeter (DSC). All blends containing 30 wt% of PEGLAs showed slightly higher zero shear viscosity, higher shear thinning and increased melt elasticity (based on tan delta). Nevertheless, no significant changes in thermal properties were distinguished. High molecular weight PEGLAs were used in extrusion coating line with 3051D without problems.

Chemistry of potassium halides and their role in corrosion in biomass and waste firing

Compared to the use of traditional fossil fuels (coal, oil, natural gas), combustion of biomass and waste fuels has several environmental and economic advantages for heat and power generation. However, biomass and waste fuels might contain halogens (Cl, Br, F), alkali metals (Na, K) and heavy metals (Zn, Pb), which may cause harmful emissions and corrosion problems. Hightemperature corrosion occurs typically on furnace waterwalls and superheaters. The corrosion of the boiler tube materials limits the increase of thermal efficiency of steam boilers and leads to costly shutdowns and repairs. In recent years, some concerns have been raised about halogen (Cl, Br, and F)-related hightemperature corrosion in biomass- and waste-fired boilers. Chlorine-related high-temperature corrosion has been studied extensively. The presence of alkali chlorides in the deposits is believed to play a major role in the corrosion observed in biomass and waste fired boilers. However, there is much less information found in literature on the corrosion effect of bromine and fluorine. According to the literature, bromine is only assumed to play a role similar to chlorine; the role of fluorine is even less understood. In this work, a series of bubbling fluidized bed (BFB) bench-scale tests were carried out to characterize the formation and sulfation behaviors of KCl and KBr in BFB combustion conditions. Furthermore, a series of laboratory tests were carried out to investigate the hightemperature corrosion behaviors of three different superheater steels (10CrMo9-10, AISI 347 and Sanicro 28) exposed to potassium halides in ambient air and wet air (containing 30% H2O). The influence of H2O and O2 on the high-temperature corrosion of steels both with and without a salt (KCl) in three gas atmospheres (2% H2O-30% O2-N2, 2% H2O-2% O2-N2 and 30% H2O-2% O2-N2) was also studied. From the bench-scale BFB combustion tests, it was found that HBr has a clearly higher affinity for the available K forming KBr than HCl forming KCl. The tests also indicated that KCl has a higher tendency for sulfation than KBr. From the laboratory corrosion tests in ambient air (also called “dry air” in Paper III and Paper IV), it was found that at relatively low temperatures (≤ 550 °C) the corrosivity of KBr and KF are similar to KCl. At 600 °C, KF showed much stronger corrosivity than KBr and KCl, especially for 10CrMo9-10 and AISI 347. When exposed to KBr or KF, 10CrMo9-10 was durable at least up to 450 °C, while AISI 347 and Sanicro 28 were durable at least up to 550 °C. From the laboratory corrosion tests in wet air (30% H2O), no obvious effect of water vapor was detected at 450 °C. At 550 °C, the influence of water vapor became significant in some cases, but the trend was not consistent. At 550 °C, after exposure with KBr, 10CrMo9-10 suffered from extreme corrosion; after exposure with KF and KCl, the corrosion was less severe, but still high. At 550 °C, local deep pitting corrosion occurred on AISI 347 and Sanicro 28 after exposure with KF. Some formation of K2CrO4 was observed in the oxide layer. At 550 °C, AISI 347 and Sanicro 28 suffered from low corrosion (oxide layer thickness of < 10 μm) after exposure with KBr and KCl. No formation of K2CrO4 was observed. Internal oxidation occurred in the cases of AISI 347 with KBr and KCl. From the laboratory corrosion tests in three different gas atmospheres (2% H2O-30% O2-N2, 2% H2O-2% O2-N2 and 30% H2O-2% O2-N2), it was found that in tests with no salt, no corrosion occurred on AISI 347 and Sanicro 28 up to 600 °C in both the “O2-rich” (2% H2O-30% O2-N2) and “H2O-rich” (30% H2O-2% O2-N2) gas atmospheres; only 10CrMo9-10 showed increased corrosion with increasing temperature. For 10CrMo9-10 in the “O2-rich” atmosphere, the presence of KCl significantly increased the corrosion compared to the “no salt” cases. For 10CrMo9-10 in the “H2O-rich” atmosphere, the presence or absence of KCl did not show any big influence on corrosion. The formation of K2CrO4 was observed only in the case with the “O2-rich” atmosphere. Considering both the results from the BFB tests and the laboratory corrosion tests, if fuels containing Br were to be combusted, the corrosion damage of superheaters would be expected to be higher than if the fuels contain only Cl. Information generated from these studies can be used to help the boiler manufacturers in selecting materials for the most demanding combustion systems.

Preparative ion exchange for salt solutions

Työssä tutkittiin moniarvoisten metalliformiaattien valmistusta ioninvaihto-menetelmällä. Kirjallisuustutkimus käsitteleetunnettuja alumiiniformiaatin ja rautaformiaatin valmistusmenetelmiä, kationinvaihtohartsien ominaisuuksia, ioninvaihtohartsien selektiivisyyttä ja alumiinin, raudan, magnesiumin ja sinkin vesikemiaa. Laboratoriokokeiden avulla tutkittiin sinkki-, magnesium-, rauta(II)- ja alumiiniformiaattien valmistusta ioninvaihdolla. Kokeet suoritettiin kolonnissa, joka oli pakattu makrohuokoisella tai geelimäisellä vahvalla kationin-vaihtohartsilla. Hartsi vaihdettiin natriummuodosta metallimuotoon metallikloridi- tai metallisulfaattiliuoksella.Metalli eluoitiin hartsista natriumformiaatilla. Formiaattien valmistus onnistui makrohuokoista vahvaa kationinvaihtohartsia käyttämällä. Rauta(II)formiaatin valmistus oli vaikeampaa kuin muiden formiaattien, koska rauta(II) hapettui osittain rauta(III):ksi valmistuksen aikana. Alumiiniformiaattia valmistettiin käyttäen sekä makrohuokoista että geelimäistä hartsia. Makrohuokoisen hartsin havaittiin soveltuvan geelimäistä hartsia paremmin alumiiniformiaatin valmistukseen. Kungeelimäistä hartsia käytettiin, noin 30 % alumiinista jäi kiinni hartsiin eikä siten eluoitunut. Ioninvaihdon selektiivisyyskertoimien saamiseksi suoritettiin tasapainokokeita. Selektiivisyyskertoimia käytettiin ioninvaihtokolonnin dynaamisessa simuloinnissa. Ioninvaihdon simuloiminen dynaamisella kolonnimallilla onnistui hyvin.

Ion-exchange resins as stationary phase in reactive chromatography

Dynamic behavior of bothisothermal and non-isothermal single-column chromatographic reactors with an ion-exchange resin as the stationary phase was investigated. The reactor performance was interpreted by using results obtained when studying the effect of the resin properties on the equilibrium and kinetic phenomena occurring simultaneously in the reactor. Mathematical models were derived for each phenomenon and combined to simulate the chromatographic reactor. The phenomena studied includes phase equilibria in multicomponent liquid mixture¿ion-exchange resin systems, chemicalequilibrium in the presence of a resin catalyst, diffusion of liquids in gel-type and macroporous resins, and chemical reaction kinetics. Above all, attention was paid to the swelling behavior of the resins and how it affects the kinetic phenomena. Several poly(styrene-co-divinylbenzene) resins with different cross-link densities and internal porosities were used. Esterification of acetic acid with ethanol to produce ethyl acetate and water was used as a model reaction system. Choosing an ion-exchange resin with a low cross-link density is beneficial inthe case of the present reaction system: the amount of ethyl acetate as well the ethyl acetate to water mole ratio in the effluent stream increase with decreasing cross-link density. The enhanced performance of the reactor is mainly attributed to increasing reaction rate, which in turn originates from the phase equilibrium behavior of the system. Also mass transfer considerations favor the use ofresins with low cross-link density. The diffusion coefficients of liquids in the gel-type ion-exchange resins were found to fall rapidly when the extent of swelling became low. Glass transition of the polymer was not found to significantlyretard the diffusion in sulfonated PS¿DVB ion-exchange resins. It was also shown that non-isothermal operation of a chromatographic reactor could be used to significantly enhance the reactor performance. In the case of the exothermic modelreaction system and a near-adiabatic column, a positive thermal wave (higher temperature than in the initial state) was found to travel together with the reactive front. This further increased the conversion of the reactants. Diffusion-induced volume changes of the ion-exchange resins were studied in a flow-through cell. It was shown that describing the swelling and shrinking kinetics of the particles calls for a mass transfer model that explicitly includes the limited expansibility of the polymer network. A good description of the process was obtained by combining the generalized Maxwell-Stefan approach and an activity model that was derived from the thermodynamics of polymer solutions and gels. The swelling pressure in the resin phase was evaluated by using a non-Gaussian expression forthe polymer chain length distribution. Dimensional changes of the resin particles necessitate the use of non-standard mathematical tools for dynamic simulations. A transformed coordinate system, where the mass of the polymer was used as a spatial variable, was applied when simulating the chromatographic reactor columns as well as the swelling and shrinking kinetics of the resin particles. Shrinking of the particles in a column leads to formation of dead volume on top of the resin bed. In ordinary Eulerian coordinates, this results in a moving discontinuity that in turn causes numerical difficulties in the solution of the PDE system. The motion of the discontinuity was eliminated by spanning two calculation grids in the column that overlapped at the top of the resin bed. The reactive and non-reactive phase equilibrium data were correlated with a model derived from thethermodynamics of polymer solution and gels. The thermodynamic approach used inthis work is best suited at high degrees of swelling because the polymer matrixmay be in the glassy state when the extent of swelling is low.

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.

Modeling of water/steam circulation in Circulating Fluidized Bed boiler

A distinctive design feature of steam boiler with natural circulation is the presence of the steam drum which plays a role of the separator of vapor from the flow of water-and-steam mixture coming into steam drum from the furnace tubes. Steam drum with unheated downcomer tubes, deducing from it, and riser (screen/furnace tubes) inside the furnace is a closed circulation loop in which movement of water (downcomer tubes) and water-and-steam mixture (riser tubes) is organized. The movement of the working fluid is appears due to occurrence of the natural pressure, determined by the difference in hydrostatic pressure and the mass of water and water-and-steam mixtures in downcomer and riser tubes and called the driving pressure of the natural circulation:

Modeling of water/steam circulation in Circulating Fluidized Bed boiler

A distinctive design feature of steam boiler with natural circulation is the presence of the steam drum which plays a role of the separator of vapor from the flow of water-and-steam mixture coming into steam drum from the furnace tubes. Steam drum with unheated downcomer tubes, deducing from it, and riser (screen/furnace tubes) inside the furnace is a closed circulation loop in which movement of water (downcomer tubes) and water-and-steam mixture (riser tubes) is organized. The movement of the working fluid is appears due to occurrence of the natural pressure, determined by the difference in hydrostatic pressure and the mass of water and water-and-steam mixtures in downcomer and riser tubes and called the driving pressure of the natural circulation: S drive = H steam (ρ down + ρ mix) g where: ρ down - density of water in downcomer tubes; ρ mix - density of water in riser tubes; H steam - height of steam content section; g - acceleration of gravity. In steam boilers with natural circulation the circulation rate is usually between 10 and 30. Thus, consumption of water in the circulation circuit “circulation rate times” more than steam output of the boiler. There are two aspects of the design of natural water circulation loops. One is to ensure a sufficient mass flux of circulating water to avoid burnout of evaporator tubes. The other is to avoid tube wall temperature fluctuation and tube vibration due to oscillation of circulation velocity. The design criteria are therefore reduced, in principle, to those of critical heat flux, critical flow rate for burnout, and flow instability. In practical design, however, the circulation velocity and the void fraction at the evaporator tube outlet are used as the design criteria (Seikan I., et. al., 1999). This study has been made with assumption that the heat flux in the furnace of the boiler even all the time. The target of the study was to define the circulation rate of the boiler, thus average heat flux do not change it. I would like to acknowledge professionals from “Foster Wheeler” company for good and comfortable cooperation.