Titanium dioxide based nanomaterials for photocatalytic water treatment

Water treatment using photocatalysis has gained extensive attention in recent years. Photocatalysis is promising technology from green chemistry point of view. The most widely studied and used photocatalyst for decomposition of pollutants in water under ultraviolet irradiation is TiO2 because it is not toxic, relatively cheap and highly active in various reactions. Within this thesis unmodified and modified TiO2 materials (powders and thin films) were prepared. Physico-chemical properties of photocatalytic materials were characterized with UV-visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometry (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), ellipsometry, time-of-flight secondary ion mass spectrometry (ToF-SIMS), Raman spectroscopy, goniometry, diffuse reflectance measurements, thermogravimetric analysis (TGA) and nitrogen adsorption/desorption. Photocatalytic activity of prepared samples in aqueous environment was tested using model compounds such as phenol, formic acid and metazachlor. Also purification of real pulp and paper wastewater effluent was studied. Concentration of chosen pollutants was measured with high pressure liquid chromatography (HPLC). Mineralization and oxidation of organic contaminants were monitored with total organic carbon (TOC) and chemical oxygen demand (COD) analysis. Titanium dioxide powders prepared via sol-gel method and doped with dysprosium and praseodymium were photocatalytically active for decomposition of metazachlor. The highest degradation rate of metazachlor was observed when Pr-TiO2 treated at 450ºC (8h) was used. The photocatalytic LED-based treatment of wastewater effluent from plywood mill using commercially available TiO2 was demonstrated to be promising post-treatment method (72% of COD and 60% of TOC was decreased after 60 min of irradiation). The TiO2 coatings prepared by atomic layer deposition technique on aluminium foam were photocatalytically active for degradation of formic and phenol, however suppression of activity was observed. Photocatalytic activity of TiO2/SiO2 films doped with gold bipyramid-like nanoparticles was about two times higher than reference, which was not the case when gold nanospheres were used.

Assessing the Environmental Value of Water Treatment Solutions in the Mining Industry

Environmental accountability has become a major source of competitive advantage for industrial companies, because customers consider it as relevant buying criterion. However, in order to leverage their environmental responsibility, industrial suppliers have to be able to demonstrate the environmental value of their products and services, which is also the aim of Kemira, a global water chemistry company considered in this study. The aim of this thesis is to develop a tool which Kemira can use to assess the environmental value of their solutions for the customer companies in mining industry. This study answers to questions on what kinds of methods to assess environmental impacts exist, and what kind of tool could be used to assess the environmental value of Kemira’s water treatment solutions. The environmental impacts of mining activities vary greatly between different mines. Generally the major impacts include the water related issues and wastes. Energy consumption is also a significant environmental aspect. Water related issues include water consumption and impacts in water quality. There are several methods to assess environmental impacts, for example life cycle assessment, eco-efficiency tools, footprint calculations and process simulation. In addition the corresponding financial value may be estimated utilizing monetary assessment methods. Some of the industrial companies considered in the analysis of industry best practices use environmental and sustainability assessments. Based on the theoretical research and conducted interviews, an Excel based tool utilizing reference data on previous customer cases and customer specific test results was considered to be most suitable to assess the environmental value of Kemira’s solutions. The tool can be used to demonstrate the functionality of Kemira’s solutions in customers’ processes, their impacts in other process parameters and their environmental and financial aspects. In the future, the tool may be applied to fit also Kemira’s other segments, not only mining industry.

Developing Service-based Solutions for Water Treatment in Finnish Mining Industry

The aim of this master’s thesis is to analyze the mining industry customers' current and future needs for the water treatment services and discover new business development opportunities in the context of mine water treatment. In addition, the study focuses on specifying service offerings needed and evaluate suitable revenue generation models for them. The main research question of the study is: What kind of service needs related to water treatment can be identified in the Finnish mining industry? The literature examined in the study focused on industrial service classification and new service development process as well as the revenue generation of services. A qualitative research approach employing a case study method was chosen for the study. The present study uses customer and expert interviews as primary data source, complemented by archival data. The primary data was gathered by organizing total of 13 interviews, and the interviews were analyzed by using qualitative content analysis. The abductive-logic was chosen as the way of conducting scientific reasoning in this study. As a result, new service proposals were developed for Finnish mine industry suppliers. The main areas of development were on asset efficiency services and process support services. The service needs were strongly associated with suppliers’ know-how of water treatment process optimization, cost-effectiveness as well as on alternative technologies. The study provides an insight for managers that wish to pursue a water treatment services as a part of their business offering.

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Painovoimaisen kemiallisen vesienkäsittelymenetelmän soveltuvuus pienille turvetuotantoalueille

Turvetuotannon suurimpana ympäristövaikutuksena pidetään tuotantoalueiden valuma-vesistä johtuvia ympäristövaikutuksia. Tiukentunut ympäristölainsäädäntö edellyttää uusilta turvetuotantoalueilta parhaan käyttökelpoisen tekniikan käyttöä valumavesien-käsittelyssä. Parhaaksi käyttökelpoiseksi tekniikaksi luetaan pintavalutus- ja kasvilli-suuskentän sekä kemikaloinnin käyttö valumavesien puhdistuksessa. Tämän tutkimuksen tarkoituksena oli selvittää painovoimaisen kemiallisen vesienkäsit-telymenetelmän soveltuvuutta pienille turvetuotantoalueille. Tutkimuskohteena oli Lep-pisuo Luumäen kunnassa, jonne rakennettiin 2010 painovoimaisen kemikaloinnin koe-laitteisto. Laitteiston puhdistustulosta tarkasteltiin kemikalointiin tulevan ja lähtevän veden sekä taustanäytepisteiden tarkkailutulosten avulla. Laitteiston toimivuutta arvioi-tiin kemikaalin annostelun ja toimintavarmuuden avulla. Vuoden 2010 tarkkailutuloksista saatiin keskimääräisiksi erotustehokkuuksiksi koko-naisfosforin osalta 65,2 %, kokonaistypen osalta 28,1 % ja CODMn osalta 65,5 %. Ke-mikaloinnista lähtevän veden kokonaisfosforipitoisuus oli 7,7 μg/l, kokonaistyppipitoi-suus 656 μg/l ja CODMn 5,5 mg/l O2. Ferrisulfaatin annostelu oli keskimäärin 81 mg/l, vaihteluvälillä 25–268 mg/l.

Sähkökoagulaatiolaitteiston kehittäminen pintakäsittelylaitoksen jäteveden käsittelyyn

Tässä työssä kehitetään sähkökoagulaatiolaitteisto metallipinnoituslaitoksen jätevesien puhdistamiseen. Sähkökoagulaatio on sähkökemiallinen vedenpuhdistusprosessi, jossa hyödynnetään liukenevaa metallianodia. Sähkövirta irrottaa anodilta metalli-ioneja, jotka yhdistyvät vapaiden hydroksidi-ionien kanssa. Syntyneet metallihydroksidit vetävät puoleensa veden epäpuhtauksia ja saostuvat. Tämän työn tavoitteena oli kehittää sähkökoagulaatiolaitteistosta korvaaja käytössä olleelle kemialliselle jätevedenpuhdistuslaitteistolle. Sähkökoaglaatiolaitteiston toivottiin parantavan jätevedenpuhdistuksen toimintavarmuutta ja pienentävän käyttökustannuksia. Prototyyppilaitteistolla suoritettujen kokeiden perusteella sähkökoagulaation todettiin olevan kemiallista jätevedenkäsittelyä toimintavarmempi. Käyttökustannusten todettiin olevan samaa tasoa tai korkeammat kuin kemiallisella menetelmällä. Laitteiston suunnittelussa sovellettiin järjestelmällistä koneensuunnittelua. Suunnittelussa saavutettiin sille asetetut tavoitteet. Osatoiminnoille löydettiin toimivat ratkaisut ja laite on helposti huollettavissa.

Pintavalutuskentän ja kemikalointiaseman soveltuvuus turvetuotantoalueille

Tässä kandidaatintyössä tutkittiin kahden eri vesiensuojelurakenteen toimivuutta ja soveltuvuutta turvetuotantoalueelle. Työn tavoitteena oli vertailla pintavalutuskentän ja kemiallisen vedenkäsittelyn eroavaisuuksia toiminnoiltaan ja puhdistustehoiltaan. Lisäksi työn tavoitteena oli tarkastella parhaimman vesiensuojelurakenteen valintaan vaikuttavia tekijöitä. Työ toteutettiin vertailemalla Vapo Oy:n tarkkailuraporteista sekä turvetuotantoalueiden ominaiskuormitusselvityksistä koottuja tilastoja. Vertailu suoritettiin puhdistustulosten ja kuormituslukujen avulla. Tuotantoaluekohtaisia tarkkailuraportteja oli käytettävissä kolmelta edeltävältä vuodelta ja työssä käytetty ominaiskuormitusselvitys oli koonti vuosien 2008–2012 tuloksista. Työstä saadut tulokset tukevat vesiensuojelumenetelmistä jo saatavilla olevaa teoriaa. Turvetuotantoalueelle paras käyttökelpoinen tekniikka on pintavalutuskenttä, mikä osoittautui työssä tasaisen laadukkaaksi menetelmäksi. Työssä havaittiin kemiallisen vedenkäsittelyn olevan epävarmaa ja haastavaa. Työstä saadut tulokset osoittavat käsittelyn jatkokehittämisen tarpeen.

Tertiary treatment of pulp and paper mill effluents

Työn tavoitteena oli selvittää mitä käsittelyvaihtoehtoja on olemassa jäteveden puhdistamon tertiäärikäsittelyyn ja miten suuri tarve paperi- ja selluteollisuuden prosessivesien puhdistukseen on. Tarkoituksena oli saada käsitys koko tertiäärikäsittelystä eri näkökulmista. Lopuksi läpikäytiin tertiäärikäsittelymenetelmiä ja etsittiin mahdollisia uusia menetelmiä, joita voitaisiin käyttää jäteveden tertiääripuhdistukseen. Ensimmäisenä työssä on perehdytty jäteveden koostumukseen paperi- ja selluteollisuudessa ja puhdistukseen ilmastetulla aktiivilietemenetelmällä, jotta tertiäärikäsittely ymmärrettäisiin konseptina paremmin. Lisäksi työssä selvitettiin tertiäärikäsittelyn tarvetta ja vaihtoehtoja sen käyttämättä jättämiselle teollisuuden ja muun ympäristöä vahingoittavan toiminnan ympäristönäkökohdat huomioonottaen. Lyhyiden menetelmäesitysten jälkeen kiteytetään tertiäärikäsittelyn ympäristönäkökohdatja vaihtoehdot sen käytölle yhteenvetona, jossa otetaan huomioon myös viranomaisten, yrityksen ja BAT referenssien sisältämä tieto tertiäärikäsittelystä. Työn kokeellinen osa sisältää erään tertiäärikäsittelysovelluksenrakentamisen, koekäytön ja laboratorioanalyysien yhteenvedon. Lisäksi menetelmää verrataan kustannus-tehokkuudeltaan vastaavien menetelmien kanssa. Tarkoituksena oli löytää jäteveden tertiäärikäsittelyyn sopiva laitteisto, jonka toimintaanei sisältyisi kemikaalien annostelua ja sitä käytettäisiin lähinnä jätevedenpuhdistamon ongelmatilanteiden väliaikaiseksi ratkaisuksi. Mahdollisesti se voisi toimia myös jatkuvatoimisesti veden kirkastuksessa. Diplomityössä rakennettu laitteisto, jota käytettiin myös pilot koeajoissa, ei ollut paras mahdollinen laitteisto tertiäärikäsittelyn toteuttamiseksi paperi- ja selluteollisuudessa, mutta kilpailukykyinen muiden laitteistojen kanssa. Laitteiston toimintaperiaate on kuitenkin käyttökelpoinen tietyin varauksin ja sitä voidaan käyttää vedenpuhdistamiseen.

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.

Electrocoagulation in the treatment of industrial waters and wastewaters

Chemical coagulation is commonly used in raw water and wastewater treatment plants for the destabilisation of pollutants so that they can be removed in the subsequent separation processes. The most commonly used coagulation chemicals are aluminium and iron metal salts. Electrocoagulation technology has also been proposed for the treatment of raw waters and wastewaters. With this technology, metal cations are produced on the electrodes via electrolysis and these cations form various hydroxides in the water depending on the water pH. In addition to this main reaction, several side reactions, such as hydrogen bubble formation and the reduction of metals on cathodes, also take place in the cell. In this research, the applications of electrocoagulation were investigated in raw water treatment and wastewater applications. The surface water used in this research contained high concentrations of natural organic matter (NOM). The effect of the main parameters – current density, initial pH, electric charge per volume, temperature and electrolysis cell construction – on NOM removal were investigated. In the wastewater treatment studies, the removal of malodorous sulphides and toxic compounds from the wastewaters and debarking effluents were studied. Also, the main parameters of the treatment, such as initial pH and current density, were investigated. Aluminium electrodes were selected for the raw water treatment, whereas wastewaters and debarking effluent were treated with iron electrodes. According to results of this study, aluminium is more suitable electrode material for electrocoagulation applications because it produces Al(III) species. Metal ions and hydroxides produced by iron electrodes are less effective in the destabilisation of pollutants because iron electrodes produce more soluble and less charged Fe(II) species. However, Fe(II) can be effective in some special applications, such as sulphide removal. The resulting metal concentration is the main parameter affecting destabilisation of pollutants. Current density, treatment time, temperature and electrolysis cell construction affect the dissolution of electrodes and hence also the removal of pollutants. However, it seems that these parameters have minimal significance in the destabilization of the pollutants besides this effect (in the studied range of parameters). Initial pH and final pH have an effect on the dissolution of electrodes, but they also define what aluminium or iron species are formed in the solution and have an effect on the ζ-potential of all charged species in the solution. According to the results of this study, destabilisation mechanisms of pollutants by electrocoagulation and chemical coagulation are similar. Optimum DOC removal and low residual aluminium can be obtained simultaneously with electrocoagulation, which may be a significant benefit of electrocoagulation in surface water treatment compared to chemical coagulation. Surface water treatment with electrocoagulation can produce high quality water, which could be used as potable water or fresh water for industrial applications. In wastewater treatment applications, electrocoagulation can be used to precipitate malodorous sulphides to prevent their release into air. Technology seems to be able to remove some toxic pollutants from wastewater and could be used as pretreatment prior to treatment at a biological wastewater treatment plant. However, a thorough economic and ecological comparison of chemical coagulation and electrocoagulation is recommended, because these methods seem to be similar in pollutant destabilisation mechanisms, metal consumption and removal efficiency in most applications.

Tertiary Treatment and Re-use of Kraft Pulp Mill Effluent

The efficient use of materials and natural recourses, for ecological and economic reasons, has become more and more important in all industries. In the forest industries this means higher levels of closure in the material circulations of the mills. One possibility to reduce wastewater discharge is to re-use part of the 2nd clarifier effluent as process water. The main target of this thesis was to evaluate the technical suitability of several mechanical and chemical tertiary treatment methods for water re-use. Some of the tested methods seemed to have high potential for the removal of some specific constituents from the wastewater. Tertiary treatment is needed because higher levels of closure may cause problems with increasing amounts of non-process elements in different points of kraft pulp process. The aspect of sustainable development was taken into account by evaluating positive and negative environmental effects of the treatment processes. Environmental benefits can be gained by using some of the tertiary treatment methods tested. These methods should still be researched more for system optimization.

International Advanced Water Technologies Centre, IAWTC/LADEC and LUT 2013 : Questionnaire Responses from Russian Drinking Water and Wastewater Treatment Plants

In this report, information is published concerning Russian water and wastewater treatment plants. The information is based on a questionnaire sent to 70 water and wastewater treatment plants in 2012-2013. The questionnaire was prepared by the International Advanced Water Technologies Centre (IAWTC) and Lahti Development Company (LADEC). The questions dealt with an assessment of the present state, the need for changes, renovation, investments, and how to improve the efficiency of the operation by training and investments. A significant need to renew the old pipelines, constructions, and processes was clearly evident. The aggregated answers can be utilized in Russia as internal benchmarking in order to arrange training and plant visits, which were requested in many of the answers. Sharing this open report with the respondents can aid networking and awareness of HELCOM requirements which relate to waste water treatment plants discharging their waste water directly or indirectly into the Baltic Sea. The aim of this report is to provide information for Finnish small and medium size companies (SMEs) as regards possible water related exportation to different parts of Russia.

Sellu ja paperiteollisuuden jätevesien tertiäärikäsittelyn kemikaloinnin optimointi

Kuluneen vuosikymmenen aikana metsäteollisuuden päästöt ympäristöön ovat pienentyneet huomattavasti tuotantomäärien kasvustahuolimatta. Lainsäädännön myötä lupa-arvot tiukentuvat edelleen joten olemassa olevia puhdistus prosesseja on parannettava ja niiden rinnalle on kehitettävä uusia, yhä tehokkaampia menetelmiä. Aquaflow Oy suunnittelee jäteveden puhdistamoja sellu- ja paperiteollisuuteen. Kilpailun kiristyessä kilpailuetua haetaan jatkuvan kehittymisen kautta. Yhä useammilla jäteveden puhdistamoilla tarvitaan teriäärikäsittely biohajoamattoman aineksen poistamiseen. Tertiäärikäsittely on käyttökustannuksiltaan kallis kemikaali kulutuksensa vuoksi. Tässä työssä pyrittiin optimoimaan tertiääriprosessin kemikaalien syöttöä. Lisäksi selvitettiin millaisissa oloissa keskeiset saostus ja flokkaus prosessit toimivatparhaiten, sekä mitkä tekijät vaikuttavat merkittävästi jäteveden kemiallisen käsittelyn tulokseen. Saatujen tulosten perusteella kemikaalien sekoituksen tehostuksen seurauksena kemikaali määriä voidaan pienentää, samalla puhdistustulos paranee ja jäännöskemikaalien määrä pienenee. pH:n säätö on olennainen osa prosessin toiminnan kannalta, jos pH ei ole kemikaalien toiminta alueella ei puhdistusta tapahdu ja kemikaalit kulkeutuvat luontoon. Tertiäärikäsittelyyn tulevan jäteveden online seurannan avulla juuri oikea kemikaaliannos olisihelpompaa määrittää kuin päivän viiveellä tulevien laboratorio analyysien perusteella ja yli-/ali annostukselta vältyttäisiin

Wet Oxidation of Concentrated Wastewaters: Process Combination and Reaction Kinetic Modeling

The accumulation of aqueous pollutants is becoming a global problem. The search for suitable methods and/or combinations of water treatment processes is a task that can slow down and stop the process of water pollution. In this work, the method of wet oxidation was considered as an appropriate technique for the elimination of the impurities present in paper mill process waters. It has been shown that, when combined with traditional wastewater treatment processes, wet oxidation offers many advantages. The combination of coagulation and wet oxidation offers a new opportunity for the improvement of the quality of wastewater designated for discharge or recycling. First of all, the utilization of coagulated sludge via wet oxidation provides a conditioning process for the sludge, i.e. dewatering, which is rather difficult to carry out with untreated waste. Secondly, Fe2(SO4)3, which is employed earlier as a coagulant, transforms the conventional wet oxidation process into a catalytic one. The use of coagulation as the post-treatment for wet oxidation can offer the possibility of the brown hue that usually accompanies the partial oxidation to be reduced. As a result, the supernatant is less colored and also contains a rather low amount of Fe ions to beconsidered for recycling inside mills. The thickened part that consists of metal ions is then recycled back to the wet oxidation system. It was also observed that wet oxidation is favorable for the degradation of pitch substances (LWEs) and lignin that are present in the process waters of paper mills. Rather low operating temperatures are needed for wet oxidation in order to destruct LWEs. The oxidation in the alkaline media provides not only the faster elimination of pitch and lignin but also significantly improves the biodegradable characteristics of wastewater that contains lignin and pitch substances. During the course of the kinetic studies, a model, which can predict the enhancements of the biodegradability of wastewater, was elaborated. The model includes lumped concentrations suchas the chemical oxygen demand and biochemical oxygen demand and reflects a generalized reaction network of oxidative transformations. Later developments incorporated a new lump, the immediately available biochemical oxygen demand, which increased the fidelity of the predictions made by the model. Since changes in biodegradability occur simultaneously with the destruction of LWEs, an attempt was made to combine these two facts for modeling purposes.

Kalvoerotusprosessin esikäsittely

Työn tavoitteena oli tutkia kiertoveden puhdistamiseen käytetyn kalvosuodatuksen esikäsittelymenetelmien vaikutusta ultrasuodatukseen. Suodatettava vesi oli kierrätyskuitua käyttävän paperikoneen kiekkosuotimen kirkassuodosta. Koeajon loppuosassa käytettiin biokirkassuodosta. Paperitehtaassa oli suljettu vesikierto. Pilot-laitteistona käytettiin Metso PaperChemin OptiFilter CR550/40 ultrasuodatusyksikköä. Testatut kalvot olivat C30 kalvoja. Suodatuksissa seurattiin esikäsittelymenetelmien vaikutusta permeaatin määrään ja laatuun. Ultrasuodatus tehtiin sekä ilman esikäsittelyä että lamelliselkeytin esikäsittelynä. Esikäsittelykemikaalina käytettiin talkkia. Ultrasuodatuksissa havaittiin, että suodatuslämpötilalla oli suora vaikutus kapasiteettiin. Lämpötila vaikutti lineaarisesti kirkassuodoksen ja biokirkassuodoksen permeaattivuohon. Lämpötila nostettiin 55oC:een suodatuslämpötilasta 35 – 40oC. Korkeassa lämpötilassa kirkassuodos oli kapasiteetiltaan suurempi kuin biokirkassuodos. Konsentrointiajoista nähtiin, että ultrasuodatuksen syötön konsentraatioaste vaikutti kirkassuodoksen permeaattivuohon. Syötön konsentraatioastetta lisättäessä kapasiteetti laski. Konsentrointiajoja vertailtaessa havaitaan, että ilman esikäsittelyä vuo laski konsentroitaessa nopeammin kuin suodatuksissa, joissa käytettiin esikäsittelyä. Lamelliselkeyttimellä ja talkilla esikäsitelty suodatus laski kapasiteettia vähiten. Konsentraatioasteen nostaminen lisäsi konsentraatin kemiallista hapenkulutusta. Konsentraatin viskositeetti nousi konsentraatioastetta lisättäessä. Analyysitulosten perusteella saadaan ultrasuodatuskalvoille tyypilliset reduktiot. COD-reduktio oli 10 – 30 %, anionisuuden 40 – 70 % ja värin 80 – 90 %. Vuon kanssa korreloivat pH, uuteaine, ligniini, viskositeetti ja hemiselluloosat.