Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

Synthesis of percarboxylic acids in microreactor

Percarboxylic acids are commonly used as disinfection and bleaching agents in textile, paper, and fine chemical industries. All of these applications are based on the oxidative potential of these compounds. In spite of high interest in these chemicals, they are unstable and explosive chemicals, which increase the risk of synthesis processes and transportation. Therefore, the safety criteria in the production process should be considered. Microreactors represent a technology that efficiently utilizes safety advantages resulting from small scale. Therefore, microreactor technology was used in the synthesis of peracetic acid and performic acid. These percarboxylic acids were produced at different temperatures, residence times and catalyst i.e. sulfuric acid concentrations. Both synthesis reactions seemed to be rather fast because with performic acid equilibrium was reached in 4 min at 313 K and with peracetic acid in 10 min at 343 K. In addition, the experimental results were used to study the kinetics of the formation of performic acid and peracetic acid. The advantages of the microreactors in this study were the efficient temperature control even in very exothermic reaction and good mixing due to the short diffusion distances. Therefore, reaction rates were determined with high accuracy. Three different models were considered in order to estimate the kinetic parameters such as reaction rate constants and activation energies. From these three models, the laminar flow model with radial velocity distribution gave most precise parameters. However, sulfuric acid creates many drawbacks in this synthesis process. Therefore, a ´´greener´´ way to use heterogeneous catalyst in the synthesis of performic acid in microreactor was studied. The cation exchange resin, Dowex 50 Wx8, presented very high activity and a long life time in this reaction. In the presence of this catalyst, the equilibrium was reached in 120 second at 313 K which indicates a rather fast reaction. In addition, the safety advantages of microreactors were investigated in this study. Four different conventional methods were used. Production of peracetic acid was used as a test case, and the safety of one conventional batch process was compared with an on-site continuous microprocess. It was found that the conventional methods for the analysis of process safety might not be reliable and adequate for radically novel technology, such as microreactors. This is understandable because the conventional methods are partly based on experience, which is very limited in connection with totally novel technology. Therefore, one checklist-based method was developed to study the safety of intensified and novel processes at the early stage of process development. The checklist was formulated using the concept of layers of protection for a chemical process. The traditional and three intensified processes of hydrogen peroxide synthesis were selected as test cases. With these real cases, it was shown that several positive and negative effects on safety can be detected in process intensification. The general claim that safety is always improved by process intensification was questioned.

Kartonkijätteestä bioetanolia - Hydrolysoitujen sokerien erotus ja väkevöinti fermentointia varten

Tässä diplomityössä tutkittiin upotettavien membraanisuodattimien soveltuvuutta sakean hydrolysaattin suodattamiseen ja esisuodatettujen sokereiden väkevöintiä membraanisuodatuksella fermentointia varten. Työssä käytettiin kierrätyskartongista entsyymien avulla valmistettua hydrolysaattia. Sakean hydrolysaatin suodattamiseen käytettiin Kubota Membranesin upposuodatusmoduuleja ja suodatuslaitteistoa. Upposuodatusmoduulien likaantumisen vähentämiseksi suodatuksissa käytettiin ilmasekoitusta ja vastavirta-pesua. Upposuodatusmoduulilla kirkastettua hydrolysaattia väkevöitiin nanosuodatuksella ja tulosta verrattiin painesuodatuksella kirkastetun hydrolysaatin nanosuodatukseen. Konsentrointisuodatusten alussa testattiin neljää nanosuodatuskalvoa hydrolysaatin konsentrointiin. Sokereiden konsentrointiin valittiin Dow FilmTecTM NF-270 nanosuodatuskalvo sen korkean sokeriretention ja hyvän vuon perusteella. Sakean hydrolysaatin esisuodatuksessa ei upotettavien membraanimoduulien ja painesuodatuksen välillä havaittu merkittäviä eroja. Työn perusteella upposuodatusmoduulien käyttö sakean hydrolysaatin suodattamisessa on kuitenkin mahdollista. Tämä mahdollistaisi sokereiden jatkuvatoimisen erottamisen hydrolysaatista. Konsentrointisuodatuksissa molemmilla esisuodatetuilla hydrolysaateilla saavutettiin yli 10 % sokerikonsentraatio ilman suurta sokerihävikkiä. Sokeriretentio pysyi myös konsentraation kasvaessa 80 % yläpuolella.

Investigation of the two-photon induced fluorescence in Rb vapour excited by Ti:Sapphire femtosecond laser pulses

In this work we report the observation of the blue visible fluorescence at 420 nm in rubidium vapour as a result of two-photon absorption excited by femtosecond laser pulses 790 nm. After experimental investigation of the spa-tial and spectral characteristics of the obtained emission we can claim that mechanism of this coherent fluorescence at 420 nm was not caused by ampli-fied spontaneous emission, but represents the nondegenerate four-wave mixing. As a probable outcome of this investigation an opportunity of creation an ultrafast all-optical switcher might appear.

Production of Mg(OH)2 from Mg-silicate rock for CO2 mineral sequestration

Sequestration of carbon dioxide in mineral rocks, also known as CO2 Capture and Mineralization (CCM), is considered to have a huge potential in stabilizing anthropogenic CO2 emissions. One of the CCM routes is the ex situ indirect gas/sold carbonation of reactive materials, such as Mg(OH)2, produced from abundantly available Mg-silicate rocks. The gas/solid carbonation method is intensively researched at Åbo Akademi University (ÅAU ), Finland because it is energetically attractive and utilizes the exothermic chemistry of Mg(OH)2 carbonation. In this thesis, a method for producing Mg(OH)2 from Mg-silicate rocks for CCM was investigated, and the process efficiency, energy and environmental impact assessed. The Mg(OH)2 process studied here was first proposed in 2008 in a Master’s Thesis by the author. At that time the process was applied to only one Mg-silicate rock (Finnish serpentinite from the Hitura nickel mine site of Finn Nickel) and the optimum process conversions, energy and environmental performance were not known. Producing Mg(OH)2 from Mg-silicate rocks involves a two-staged process of Mg extraction and Mg(OH)2 precipitation. The first stage extracts Mg and other cations by reacting pulverized serpentinite or olivine rocks with ammonium sulfate (AS) salt at 400 - 550 oC (preferably < 450 oC). In the second stage, ammonia solution reacts with the cations (extracted from the first stage after they are leached in water) to form mainly FeOOH, high purity Mg(OH)2 and aqueous (dissolved) AS. The Mg(OH)2 process described here is closed loop in nature; gaseous ammonia and water vapour are produced from the extraction stage, recovered and used as reagent for the precipitation stage. The AS reagent is thereafter recovered after the precipitation stage. The Mg extraction stage, being the conversion-determining and the most energy-intensive step of the entire CCM process chain, received a prominent attention in this study. The extraction behavior and reactivity of different rocks types (serpentinite and olivine rocks) from different locations worldwide (Australia, Finland, Lithuania, Norway and Portugal) was tested. Also, parametric evaluation was carried out to determine the optimal reaction temperature, time and chemical reagent (AS). Effects of reactor types and configuration, mixing and scale-up possibilities were also studied. The Mg(OH)2 produced can be used to convert CO2 to thermodynamically stable and environmentally benign magnesium carbonate. Therefore, the process energy and life cycle environmental performance of the ÅAU CCM technique that first produces Mg(OH)2 and the carbonates in a pressurized fluidized bed (FB) were assessed. The life cycle energy and environmental assessment approach applied in this thesis is motivated by the fact that the CCM technology should in itself offer a solution to what is both an energy and environmental problem. Results obtained in this study show that different Mg-silicate rocks react differently; olivine rocks being far less reactive than serpentinite rocks. In summary, the reactivity of Mg-silicate rocks is a function of both the chemical and physical properties of rocks. Reaction temperature and time remain important parameters to consider in process design and operation. Heat transfer properties of the reactor determine the temperature at which maximum Mg extraction is obtained. Also, an increase in reaction temperature leads to an increase in the extent of extraction, reaching a maximum yield at different temperatures depending on the reaction time. Process energy requirement for producing Mg(OH)2 from a hypothetical case of an iron-free serpentine rock is 3.62 GJ/t-CO2. This value can increase by 16 - 68% depending on the type of iron compound (FeO, Fe2O3 or Fe3O4) in the mineral. This suggests that the benefit from the potential use of FeOOH as an iron ore feedstock in iron and steelmaking should be determined by considering the energy, cost and emissions associated with the FeOOH by-product. AS recovery through crystallization is the second most energy intensive unit operation after the extraction reaction. However, the choice of mechanical vapor recompression (MVR) over the “simple evaporation” crystallization method has a potential energy savings of 15.2 GJ/t-CO2 (84 % savings). Integrating the Mg(OH)2 production method and the gas/solid carbonation process could provide up to an 25% energy offset to the CCM process energy requirements. Life cycle inventory assessment (LCIA) results show that for every ton of CO2 mineralized, the ÅAU CCM process avoids 430 - 480 kg CO2. The Mg(OH)2 process studied in this thesis has many promising features. Even at the current high energy and environmental burden, producing Mg(OH)2 from Mg-silicates can play a significant role in advancing CCM processes. However, dedicated future research and development (R&D) have potential to significantly improve the Mg(OH)2 process performance.

Recovery of carboxylic acids from aqueous streams by extraction and back extraction

Separation of carboxylic acids from aqueous streams is an important part of their manufacturing process. The aqueous solutions are usually dilute containing less than 10 % acids. Separation by distillation is difficult as the boiling points of acids are only marginally higher than that of water. Because of this distillation is not only difficult but also expensive due to the evaporation of large amounts of water. Carboxylic acids have traditionally been precipitated as calcium salts. The yields of these processes are usually relatively low and the chemical costs high. Especially the decomposition of calcium salts with sulfuric acid produces large amounts of calcium sulfate sludge. Solvent extraction has been studied as an alternative method for recovery of carboxylic acids. Solvent extraction is based on mixing of two immiscible liquids and the transfer of the wanted components form one liquid to another due to equilibrium difference. In the case of carboxylic acids, the acids are transferred from aqueous phase to organic solvent due to physical and chemical interactions. The acids and the extractant form complexes which are soluble in the organic phase. The extraction efficiency is affected by many factors, for instance initial acid concentration, type and concentration of the extractant, pH, temperature and extraction time. In this paper, the effects of initial acid concentration, type of extractant and temperature on extraction efficiency were studied. As carboxylic acids are usually the products of the processes, they are wanted to be recovered. Hence the acids have to be removed from the organic phase after the extraction. The removal of acids from the organic phase also regenerates the extractant which can be then recycled in the process. The regeneration of the extractant was studied by back-extracting i.e. stripping the acids form the organic solution into diluent sodium hydroxide solution. In the solvent regeneration, the regenerability of different extractants and the effect of initial acid concentration and temperature were studied.

Evaluation of Bubble Formation and Break Up in Suppression Pools by Using Pattern Recognition Methods

During a possible loss of coolant accident in BWRs, a large amount of steam will be released from the reactor pressure vessel to the suppression pool. Steam will be condensed into the suppression pool causing dynamic and structural loads to the pool. The formation and break up of bubbles can be measured by visual observation using a suitable pattern recognition algorithm. The aim of this study was to improve the preliminary pattern recognition algorithm, developed by Vesa Tanskanen in his doctoral dissertation, by using MATLAB. Video material from the PPOOLEX test facility, recorded during thermal stratification and mixing experiments, was used as a reference in the development of the algorithm. The developed algorithm consists of two parts: the pattern recognition of the bubbles and the analysis of recognized bubble images. The bubble recognition works well, but some errors will appear due to the complex structure of the pool. The results of the image analysis were reasonable. The volume and the surface area of the bubbles were not evaluated. Chugging frequencies calculated by using FFT fitted well into the results of oscillation frequencies measured in the experiments. The pattern recognition algorithm works in the conditions it is designed for. If the measurement configuration will be changed, some modifications have to be done. Numerous improvements are proposed for the future 3D equipment.

Feasibility of ASH DEC‐ process in treating sewage sludge and manure ash in Finland

In Finland the thermal treatment of sewage sludge has been moderate in 21th century. The reason has been the high moisture content of sludge. During 2005-2008, 97-99% of sewage sludge was utilized in landscaping and agriculture. However agricultural use has been during 2005-2007 less than 3 %. The aim of national waste management plan is that by 2016 100% of sludge is used either as soil amendment or energy. The most popular utilization method for manure is spreading it on arable land. The dry manures such as poultry manure and horse manure could also be used in incineration. The ashes could be used as fertilizers and while it is not suitable as a starter fertilizer, it is suitable in maintaining P levels in the soil. One of the main drivers for more efficient nutrient management is the eutrophication in lakes and the Baltic See. ASH DEC process can be used in concentrating phosphorus rich ashes while separating the heavy metals that could be included. ASH DEC process uses thermochemical treatment to produce renewable phosphate for fertilizer production. The process includes mixing of ashes and chlorine donors and subsequent treatment in rotary kiln for 20 min in temperature of 900 – 1 050 oC. The heavy metals evaporate and P-rich product is obtained. The toxic substances are retained in air pollution control system in form of mixed metal hydroxides. The aim of conducting this study is to estimate the potential of ASH DEC process in treating phosphorus rich ashes in Finland. The masses considered in are sewage sludge, dry manure from horses, and poultry and liquid pig manure. To date the usual treatment method for sewage sludge in Finland is composting or anaerobic digestion. Part of the amount of produced sewage sludge (800 kt/a fresh mass and 160 kt/a TS) could also be incinerated and the residual ashes used in ASH DEC process. Incinerating only manure can be economically difficult to manage because the incineration of manure is in Finland considered as waste incineration. Getting a permit for waste incineration is difficult and also small scale waste incineration is too expensive. The manure could act as an additional feedstock in counties with high density of animal husbandry where the land area might not be enough for spreading of manure. Now when the manure acts as a supplementary feedstock beside sludge, the ash can’t be used directly as fertilizer. Then it could be used in ASH DEC process. The perquisite is that the manure producers could pay for the incineration, which might prove problematic.

Morfologian hallinta nikkelin sulfidisaostuksessa

Diplomityön tarkoituksena oli tutkia nikkelin sulfidisaostuksessa syntyvien kiteiden morfologiaa ja siihen vaikuttavia parametreja. Syntyvien kiteiden kasvua ja morfologiaa tutkittiin kiteen muodostumisen ja kasvun teorioiden avulla. Saostuksen olosuhteet, kuten lämpötila, paine ja pH vaikuttavat muodostuvien kiteiden morfologiaan. Muilla parametreilla, kuten liuoksen ylikylläisyydellä, epäpuhtauksilla, lisäaineilla, sekoituksella ja reaktioajalla on myös suuri merkitys. Kokeiden avulla haluttiin liuoskoostumuksen, saostusolosuhteiden ja muiden komponenttien vaikutusta nikkelisulfidikiteiden morfologiaan. Kokeissa käytettiin kahta eri sulfidilähdettä: natriumvetysulfidia ja rikkivetyä. Puolipanoskokeissa nikkelipitoisuus oli 1,5 g/l, paine 101,3 kPa ja sekoitusnopeus 650 rpm. Saostuskokeet tehtiin natriumsulfaatti- 5 g/l ja ammoniumsulfaattiliuoksissa 300 g/l. Saostuskokeissa muuttujia olivat saostimen konsentraatio ja määrä, rauta- ja magne-siumepäpuhtaudet, lämpötila ja lisäaineet. Diplomityön kokeellisessa osassa morfologiaa tutkittiin suoraan valomikroskoopin ja pyyhkäisyelektronimikroskoopin (SEM) avulla. Morfologiaa tutkittiin myös epäsuorasti laskeutumisnopeuden, keskimääräisen partikkelikoon, ja ominaispinta-alamittausten avulla. Saostimen pitoisuuden vaikutukset partikkelimuotoon olivat pieniä, mutta vaikutukset ominaispinta-alaan ja partikkelikokoon olivat suuria. Natriumlauryylisul-faatti ja EDTA ohjasivat partikkelien rakennetta levymäisemmäksi, joka johti hitaaseen laskeutumisnopeuteen. Polyakryylihappo lisäaineena muuttaa partikkelien morfologiaa kuutiomaisemmaksi. Flokkulanttien ja raudan morfologiset vaikutukset olivat pieniä. Partikkelikoko ja omaispinta-ala pienenivät selvästi magnesiumpitoisuuden kasvaessa. Lämpötilan kasvattaminen lisäsi epäsäännöllisten kiteiden määrää ja muodostuneet kiteet olivat enemmän neulamaisia.

Värispekrien eron laskenta

Olemassa olevat spektrieromittarit eivät vastaa riittävästi CIEDE2000-värieroa. Tämän työn tavoitteena oli toteuttaa menetelmä, joka laskee värispektrien eron siten, että tulos vastaa CIEDE2000-värieroa. Kehitystyön tuloksena syntyi menetelmä, joka perustuu ennalta laskettuihin eroihin tunnettujen spektrien välillä ja niiden perusteella johdettuihin laskentaparametreihin. menetelmällä pystyy laskemaan spektrieroja vain niiden spektrien välillä, jotka saadaan sekoittamalla tunnettuja spektrejä. Laskentaparametrien laskenta on työläs prosessi ja siksi menetelmään toteutettiin hajautus usealle tietokoneelle. Menetelmä saatiin vastaamaan hyvin CIEDE2000:ia suurimmalle osalle spektrejä harvoja poikkeuksia lukuunottamatta. Ongelmat johtuvat mallissa olevasta matemaattisesta ominaisuudesta. Spektrieromittari näyttää metameerisille spektreille nollasta poikkeavan arvon, vaikka CIEDE2000 näyttää nollaa. Tämä osoittaa spektrieromittarin oikeamman toiminnan CIEDE2000-värieroon verrattuna.

Ammoniumin, fosfaatin ja nitraatin poisto adsorption avulla

Kiinnostus ravinneionien ammoniumin, fosfaatin ja nitraatin poistoon liittyy niiden ne-gatiivisiin ympäristövaikutuksiin ja niiden poistoon jätevesistä on olemassa erilaisia tekniikoita. Tässä työssä ionien poistoa tutkittiin adsorptiotekniikan avulla. Siinä perus-ajatuksena on ionin kiinnittyminen adsorbentin pintaan, jolloin sen poistaminen käsitel-tävästä vedestä on mahdollista. Tässä diplomityössä tutkittiin eri adsorbentteja ammoniumin, fosfaatin ja nitraatin poistoon, ja päämääränä oli niiden yhtäaikainen poistaminen. Kokeita tehtiin niin laboratoriossa valmistetuille ravinneliuoksille kuin Yara Suomi Oy:n Siilinjärven (Yara) toimipaikalta toimitetuille vesille. Yaran vesien osalta pääpaino oli ammoniumin poistossa. Tutkimuksen haasteina olivat ionien erilaiset varaukset, jolloin esimerkiksi positiivisesti varautunut ammoniumioni kiinnittyi negatiivisesti varautuneen adsorbentin pintaan hel-poiten. Toisaalta negatiivisesti varautuneet anionit fosfaatti ja nitraatti suosivat positiivi-sesti varautuneita adsorbentteja. Myös muiden ionin läsnäolo joko edisti tai esti adsorboitumista ja joissain tapauksissa pH:lla oli suuri merkitys prosessin onnistumiseen. Saatuja tuloksia tarkasteltiin tutkittujen ionien poistoprosenttien ja isotermimallinnuksien kautta unohtamatta muita esille tulleita seikkoja. Saatujen tulosten mukaan etenkin kalsinoitu hydrotalsiitti poisti fosfaattia ja nitraattia, mutta se ei mainittavasti toiminut ammoniumille. Ammoniumille sen sijaan toimi par-haiten zeoliitit ja bentoniitti, jotka vähensivät myös Yaran vesien ammoniumpitoisuutta. Ionien yhtäaikainen poistaminen oli haastavaa ja sen parempi ymmärtäminen edellyttää jatkotutkimuksia. Yksi jatkotutkimuskohde voisi olla eri adsorbenttien yhdistäminen keskenään, ja tästä saatiin jo alustavia, rohkaisevia tuloksia.

Täyteaineen ja tärkkelyksen annostelun optimointi paperikoneen lyhyeen kiertoon

Diplomityön tavoitteena oli selvittää tärkkelyksen ja täyteaineen annostelupaikkojen sekä – tapojen vaikutukset SC- heatset web offset -paperin ominaisuuksiin ja pintalujuuteen. Lisäksi selvitettiin, muuttuuko paperin pölyäminen annostelupaikkojen tai – tapojen vaikutuksesta. Diplomityön kirjallisuusosiossa käsiteltiin heatset web offset -painokoneen rakennetta ja sen toimintaa. Lisäksi käsiteltiin heatset web offset -painokoneella ilmenevät pölyongelmien tyypit ja, mitkä eri paperin tekijät vaikuttavat heatset web offset -painokoneen pölyämisongelmiin. Lisäksi kirjallisuusosiossa käsiteltiin yleisimmät pintalujuutta parantavat kemikaalit sekä näiden kemikaalien annostelupaikat paperikoneen lyhyeen kiertoon. Alkutason määrityksessä ja ensimmäisessä koeajossa havaittiin, että paperin huokoisuus ja huokosrakenne olivat tärkeimmät SC heatset web offset -paperin pintalujuuteen vaikuttavat tekijät. KCL:n HSWO–koepainokoneella painetuista rullista annostelutapa 4, jossa tärkkelystä ja täyteainetta annosteltiin perälaatikon syöttöpumpun imupuolelle perinteisesti, oli pintalujuudeltaan kestävin. Ahmatti-kokeissa havaittiin, että tärkkelyksen ja täyteaineen annostelu TrumpJet- laitteistolla lähempänä paperikoneen perälaatikkoa, annostelutapa 6, pienentää rullan sisäistä vetolujuushajontaa. Ahmatti -pilotkokeissa havaittiin myös, että paperin lujuusominaisuudet ja vetolujuushajonnat voitiin säilyttää entisellään, kun tärkkelystä ja täyteainetta annosteltiin perinteisesti perälaatikon syöttöpumpun imupuolelta. Toisesta koeajon koepainorullasta havaittiin KCL:n koepainatuksissa, että paperin pintalujuus heikentyy annosteltaessa tärkkelystä 8 kg/t verrattuna 10 kg/t tärkkelysannosteluun. Näiden tapojen ero ei ole merkittävä.

Permuurahaishapon valmistaminen mikroreaktorissa

Kandidaatintyön teoriaosassa perehdytään mikroreaktoreihin sekä niiden etuihin ja haasteisiin. Lisäksi esitellään lyhyesti, kuinka sekoitus näissä reaktoreissa voidaan järjestää erilaisten sekoituselementtien avulla sekä uusien ainetta lisäävien valmistusmenetelmien tarjoamat mahdollisuudet reaktorien valmistukselle. Mikroreaktorien edut liittyvät pääasiassa prosessin helpompaan hallittavuuteen, mikä johtaa mm. turvallisuuden lisääntymiseen ja energiasäästöihin. Lisäksi esitellään kokeellisessa osassa lähtöaineina käytettävät vetyperoksidi ja muurahaishappo, sekä tuotteena syntyvä permuurahaishappo ja sen käyttökohteita. Permuurahaishappoa käytetään mm. desinfiointiaineiden yhtenä komponenttina. Sitä voidaan käyttää myös paperikoneen vesikierron bakteerien tappamiseen. Epästabiiliutensa vuoksi permuurahaishappo voi räjähtää jopa huoneenlämmössä, mikä aiheuttaa merkittävän riskin sen varastoinnille ja kuljetukselle. Tästä syystä työssä tutkittu menetelmä permuurahaishapon valmistamiseksi mikroreaktorissa tarjoaa hyvän vaihtoehdon permuurahaishapon tuottamiseksi suoraan tarpeeseen. Kokeellisessa osassa permuurahaishappoa valmistettiin muurahaishaposta ja vetyperoksidista käyttäen rikkihappoa katalyyttinä reaktion nopeuttamiseksi. Lämpötilan ja viipymäajan vaikutusta tutkittiin permuurahaishapon muodostumiseen. Molempien nosto vaikutti edullisesti permuurahaishapon saantoon, mutta lämpötilan nosto lisää samalla räjähdysriskiä. Mikroreaktorissa lämpötilan nosto on kuitenkin suhteessa turvallisempaa makroreaktoriin verrattuna.

Pressure filtration characteristics of enzymatically hydrolyzed biomass suspensions

Enzymatic hydrolysis of lignocellulosic polymers is likely to become one of the key technologies enabling industrial production of liquid biofuels and chemicals from lignocellulosic biomass. Certain types of enzymes are able to hydrolyze cellulose and hemicellulose polymers to shorter units and finally to sugar monomers. These monomeric sugars are environmentally acceptable carbon sources for the production of liquid biofuels, such as bioethanol, and other chemicals, such as organic acids. Liquid biofuels in particular have been shown to contribute to the reduction of net emissions of greenhouse gases. The solid residue of enzymatic hydrolysis is composed mainly of lignin and partially degraded fibers, while the liquid phase contains the produced sugars. It is usually necessary to separate these two phases at some point after the hydrolysis stage. Pressure filtration is an efficient technique for this separation. Solid-liquid separation of biomass suspensions is difficult, because biomass solids are able to retain high amounts of water, which cannot be readily liberated by mechanical separation techniques. Most importantly, the filter cakes formed from biomaterials are compressible, which ultimately means that the separation may not be much improved by increasing the filtration pressure. The use of filter aids can therefore facilitate the filtration significantly. On the other hand, the upstream process conditions have a major influence on the filtration process. This thesis investigates how enzymatic hydrolysis and related process conditions affect the filtration properties of a cardboard suspension. The experimental work consists of pressure filtration and characterization of hydrolysates. The study provides novel information about both issues, as the relationship between enzymatic hydrolysis conditions and subsequent filtration properties has so far not been considered in academic studies. The results of the work reveal that the final degree of hydrolysis is an important factor in the filtration stage. High hydrolysis yield generally increases the average specific cake resistance. Mixing during the hydrolysis stage resulted in undefined changes in the physical properties of the solid residue, causing a high filtration resistance when the mixing intensity was high. Theoretical processing of the mixing data led to an interesting observation: the average specific cake resistance was observed to be linearly proportional to the mixer shear stress. Another finding worth attention is that the size distributions of the solids did not change very dramatically during enzymatic hydrolysis. There was an observable size reduction during the first couple of hours, but after that the size reduction was minimal. Similarly, the size distribution of the suspended solids remained almost constant when the hydrolyzed suspension was subjected to intensive mixing. It was also found that the average specific cake resistance was successfully reduced by the use of filter aids. This reduction depended on the method of how the filter aids were applied. In order to obtain high filtration capacity, it is recommended to use the body feed mode, i.e. to mix the filter aid with the slurry prior to filtration. Regarding the quality of the filtrate, precoat filtration was observed to produce a clear filtrate with negligible suspended solids content, while the body feed filtrates were turbid, irrespective of which type of filter aid was used.

Membrane development for oil contaminated water treatments

The aim of this Master’s thesis study was to develop a membrane for oil contaminated water treatments. Oily wastewaters are a big problem to environment and therefore it is important to find an efficient method for their treatment. There are several treatment methods, but one of the most promising methods is membrane filtration. In the theoretical part of this study the membrane technology and polymeric membrane preparation with phase inversion and membrane modification methods was discussed. It was also told about the most important properties of the membranes. Oily waters, their treatment methods and oily wastewater sources were discussed more specifically. In the experimental part membranes from cellulose acetate were prepared and membranes were modified with two different methods. Modification methods were surface modification and polymer mixing. The modification purpose was to make membranes more hydrophilic and increase surface charge, which can reduce fouling. Membranes were characterized by determining zeta potential, contact angle, oil retention, pure water permeability, pressure-normalized flux and fouling. It were used both synthetic and real spent oil-water emulsion in membrane filtration. Surface modification resulted membranes, which had better properties than unmodified membrane. The amount of substance used in surface modification affected a lot to membrane properties, so it would be necessary to try different amounts of substance to develop the best membrane for oil-water emulsion treatment.