Working capital management in the value chain of automotive industry

The objective of this Master’s thesis is to examine working capital management in the automotive industry in years 2006-2008. The study is conducted by the analysis of financial statements. The sample consists of 65 companies that represent different stages in the value chain of automotive industry beginning from raw material suppliers and ending to car dealers. Working capital management is studied by the cash conversion cycle (CCC). The results show that the average CCC of the value chain is 67 days. Car manufacturers had the longest CCC, 106 days, whereas the CCC of oil companies was the shortest, 22 days. The findings suggest that the cycle time of working capital usually follows the cycle time of inventories, since the changes in cycle times of accounts receivable and payable compensate each other. Improvements in working capital management could be achieved by sharing more accurate information in the chain for example about inventory levels and order points of customer. It could also be discussed within the automotive industry, if the long credit periods, which tie up working capital, are really needed. New technologies enable faster payments, which would reduce the cash conversion cycles, improve the profitability of companies, and increase the competitiveness of the value chain. Working capital should not be reduced at the expense of value chain partners, because nowadays the competition is rather between the value chains than between the companies. Similar research design is applied earlier to study working capital management in the value chain of pulp and paper industry. Even if the industries and the structures of the chains differ from each other, results were surprisingly similar. In future research, working capital management in other industries’ value chains could still be studied and compared to previous studies. ICT industry, for example, could be an interesting object.

Economics of combined power plant and pyrolysis bio-oil production

There are reasons of necessity in bio-fuel use and bio-energy fast development. It includes the material about bio-energy technologies, applications and methods. There are basic thermodynamics and economic theories. The economic calculation presents the comparison between two combinations. There are boiler plant below 20 MW in combination with ablative pyrolysis plant for bio-oil production and CHP plant below 100 MW in combination with the RTP pyrolysis bio-oil production technology. It provides a material about wood chips and bio-oil characteristics and explains it nature, presents the situation around the bio-fuel market or bio-fuel trade. There is a description of pyrolysis technologies such as ablative and RTP. The liquid product of the pyrolysis processes is bio-oil. The bio-oil could be different even of the same production process, because of the raw material nature and characteristics. The calculation shows advantages and weaknesses of combinations and obtained a proof of suppositions. The next thing, proven by this work is the fact that to get more efficiency from energy project it is good possibility to built plants in combinations.

Enhancing performance of paper coatings by tailor-made plastic pigments

The paper industry is constantly looking for new ideas for improving paper products while competition and raw material prices are increasing. Many paper products are pigment coated. Coating layer is the top layer of paper, thus by modifying coating pigment also the paper itself can be altered and value added to the final product. In this thesis, synthesis of new plastic and hybrid pigments and their performance in paper and paperboard coating is reported. Two types of plastic pigments were studied: core-shell latexes and solid beads of maleimide copolymers. Core-shell latexes with partially crosslinked hydrophilic polymer core of poly(n-butyl acrylate-co-methacrylic acid) and a hard hydrophobic polystyrene shell were prepared to improve the optical properties of coated paper. In addition, the effect of different crosslinkers was analyzed and the best overall performance was achieved by the use of ethylene glycol dimethacrylate (EGDMA). Furthermore, the possibility to modify core-shell latex was investigated by introducing a new polymerizable optical brightening agent, 1-[(4-vinylphenoxy)methyl]-4-(2-henylethylenyl)benzene which gave promising results. The prepared core-shell latex pigments performed smoothly also in pilot coating and printing trials. The results demonstrated that by optimizing polymer composition, the optical and surface properties of coated paper can be significantly enhanced. The optimal reaction conditions were established for thermal imidization of poly(styrene-co-maleimide) (SMI) and poly(octadecene-co-maleimide) (OMI) from respective maleic anhydride copolymer precursors and ammonia in a solvent free process. The obtained aqueous dispersions of nanoparticle copolymers exhibited glass transition temperatures (Tg) between 140-170ºC and particle sizes from 50-230 nm. Furthermore, the maleimide copolymers were evaluated in paperboard coating as additional pigments. The maleimide copolymer nanoparticles were partly imbedded into the porous coating structure and therefore the full potential of optical property enhancement for paperboard was not achieved by this method. The possibility to modify maleimide copolymers was also studied. Modifications were carried out via N-substitution by replacing part of the ammonia in the imidization reaction with amines, such as triacetonediamine (TAD), aspartic acid (ASP) and fluorinated amines (2,2,2- trifluoroethylamine, TFEA and 2,2,3,3,4,4,4-heptafluorobuthylamine, HFBA). The obtained functional nanoparticles varied in size between 50-217 nm and their Tg from 150-180ºC. During the coating process the produced plastic pigments exhibited good runnability. No significant improvements were achieved in light stability with TAD modified copolymers whereas nanoparticles modified with aspartic acid and those containing fluorinated groups showed the desired changes in surface properties of the coated paperboard. Finally, reports on preliminary studies with organic-inorganic hybrids are presented. The hybrids prepared by an in situ polymerization reaction consisted of 30 wt% poly(styrene- co-maleimide) (SMI) and high levels of 70 wt% inorganic components of kaolin and/or alumina trihydrate. Scanning Electron Microscopy (SEM) images and characterization by Fourier Transform Infrared Spcetroscopy (FTIR) and X-Ray Diffraction (XRD) revealed that the hybrids had conventional composite structure and inorganic components were covered with precipitated SMI nanoparticles attached to the surface via hydrogen bonding. In paper coating, the hybrids had a beneficial effect on increasing gloss levels.

Lämpöyrittäjäkonsepti biotuotteelle

Fossiilisista polttoaineista aiheutuvia hiilidioksidipäästöjä yritetään vähentää muun muassa lisäämällä uusiutuvien polttoaineiden käyttöä. Kiinteän biomassan ominaisuudet eroavat fossiilisesta kivihiilestä kuitenkin niin paljon, ettei biomassalla voida suoraan korvata kivihiiltä. Biomassan lämpökäsittely muuttaa sen ominaisuuksia kivihiilen kaltaiseksi, jolloin sillä on mahdollista korvata kivihiiltä. Tässä diplomityössä on tutkittu biomassan lämpökäsittelyä eli torrefiointia. Työn lähtökohtana on luoda pohjaa liikeidealle, jossa torrefioitua biomassaa tuotetaan pienissä lämpölaitoksissa lämmöntuotannon ohella. Työ sisältää laboratoriokokeita, joissa tarkastellaan käytännön kokeilla biomassan torrefioinnissa tapahtuvia ominaisuuksien muutoksia. Biomassan torrefiointiin suunnitellaan lisäksi pientä koelaitetta, jonka kokoa on mahdollista suurentaa jatkossa lämpölaitoskokoluokkaan asti. Torrefioidun biomassan tuotantokustannuksia on tarkasteltu laiteinvestointien, raaka-aine- sekä käyttökustannuksien kautta. Laboratoriokokeiden perusteella on saatu tuloksia optimaalisista toiminta-arvoista lämpökäsittelymenetelmille. Lämpöyrittäjälle on luotu perustoiminta-ajatus torrefioidun biomassan tuotannolle, jossa on tarkasteltu myös tuotannon kannattavuutta. Tämä työ antaa pohjaa aiheen jatkotutkimukselle ja -kehitykselle.

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

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

Sahan ohjausjärjestelmä myynti- ja toimitusketjun apuvälineenä sahan kannattavuuden kehittämisessä

Diplomityössä tarkasteltiin sahalaitokselle investoidun tuotannon ohjausjärjestelmän toimivuutta ja käytettävyyttä. Tutkimuksessa vertailtiin aikaisemmin suunnittelun apuna toimineita järjestelmiä uuteen ohjausjärjestelmään. Tavoitteena oli selvittää onko uuden järjestelmän sisäänajo onnistunut niin, että se tuottaisi oikeaa tietoa sahausprosessista. Tutkimuksessa tarkasteltiin myös kuinka sahan uutta ohjausjärjestelmää voitaisiin hyödyntää yrityksen myynti- ja toimitusketjun kannalta parhaiten ja huomioiden erityisesti kannattavuuslaskennallinen näkökulma. Lisäksi pohdittiin integraatiomahdollisuuksia yrityksessä käytössä oleviin muihin suunnittelujärjestelmiin. Tutkimuksen taustalla on sahateollisuuden entisestäänkin kiristynyt tilanne ja toisaalta tarve tulevaisuuden suunnitelmallisuuden parantamiseen. Kilpailussa mukana pysyminen edellyttää sahausprosessista saatavan tietomäärän keräämistä, tallentamista ja ennen kaikkea tiedon parempaa hyväksikäyttöä. Tutkimuksen kohteena ollut sahalaitos vastasi tulevaisuuden tiukentuneisiin olosuhteisiin investoimalla uuteen ohjausjärjestelmään ja uskoi siitä saatavan hyödyn auttavan heitä parantamaan sekä yksittäisten tuotteiden että koko tuotevalikoiman kannattavuutta. Ohjausjärjestelmän toivottiin tuovan todenmukaisempaa ja monipuolisempaa tietoa yrityksen suunnittelutyölle. Sahalaitoksen kannattavuuden parempi seuraaminen ja tuotevalikoiman sekä suunnittelun parempi kohdentaminen helpottuu sähköisen ohjausjärjestelmän avulla huomattavasti. Ohjausjärjestelmän kautta kannattavuuden tunnusluvut saadaan nopeammin myynti- ja toimitusketjun tietoon, poikkeamiin pystytään puuttumaan ajoissa ja yleinen tietoisuus sahausprosessista paranee. Ohjausjärjestelmän avulla mahdollistetaan entistä joustavampi koesahaus ja reklamaatioeriin porautuminen onnistuu niin ikään vaivattomammin. Yksi hyödyllinen integraatiomahdollisuus olisi SAP:n ja uuden ohjausjärjestelmän yhdistäminen, jossa hinta- ja reklamaatiotieto saataisiin yhteneväksi. Kun ohjausjärjestelmä saadaan varmuudella tuottamaan oikeaa tietoa sahausprosessista, on siitä saatava hyöty myynti- ja toimitusketjulle todellinen. Kalliin raaka-aineen entistä tehokkaampi hyödyntäminen, tuotepaletin suunnittelu ja myynnin kohdentaminen kannattavimpiin tuotteisiin, ovat tärkeä osa niitä asioita joihin järjestelmä tuo helpotusta. Tulevaisuudessa ohjausjärjestelmän jatkokehitykseen tulisi kiinnittää erityistä huomiota, jotta voitaisiin taata asiakaslähtöisyys ja kannattava tuoterakenne osana menestyksekästä liiketoimintaa.

Alternative liquid biofuels for lime kilns

Causticizing plant is an important part of kraft pulp mill. It uses green liquor from recovery boiler as a raw material and consumes lime to produce white liquor, which is an important chemical used in pulping. Lime kiln is a part of the causticizing process. It is used to convert lime mud, a by-product obtained from the causticizing back to lime in high temperatures. This conversion requires a lot of energy. The most common fuels used as energy source for lime kiln are heavy fuel oil and natural gas. In a modern pulp mill lime kiln is the only user of significant amount of fossil fuels. Replacing fossil fuels with biofuels can have prominent economical and environmental benefits. Interest in using biofuels as energy source of lime kiln has become a worldwide issue in the recent years. However fuels used for lime kiln have a lot of certain requirements. The purpose of this work is to study the required characteristics from liquid fuels used in pulp mill lime kiln and to map suitable liquid biofuels already available in the markets. Also taxation of liquid biofuels compared to heavy fuel oil in Finland, Sweden and Germany is shortly introduced.

Optimization of hydrogen plant efficiency

The purpose of this master’s thesis was to study ways to increase the operating cost-efficiency of the hydrogen production process by optimizing the process parameters while, at the same time, maintaining plant reliability and safety. The literature part reviewed other hydrogen production and purification processes as well as raw material alternatives for hydrogen production. The experimental part of the master’s thesis was conducted at Solvay Chemicals Finland Oy’s hydrogen plant in spring 2012. It was performed by changing the process parameters, first, one by one, aiming for a more efficient process with clean product gas and lower natural gas consumption. The values of the process parameters were tested based on the information from the literature, process simulation and experiences of previous similar processes. The studied parameters were reformer outlet temperature, shift converter inlet temperature and steam/carbon ratio. The results show that the optimal process conditions are a lower steam/carbon ratio and reformer outlet temperature than the current values of 3.0 and 798 °C. An increase/decrease in the shift conversion inlet temperature does not affect natural gas consumption, but it has an effect on minimizing the process steam overload.

Logistics of North-West Russia and Rail Baltica: Standpoints of Private Sector

The main aims of the present report are to describe the current state of railway transport in Russia, and to gather standpoints of Russian private transportation logistics sector towards the development of new railway connection called Rail Baltica Growth Corridor, connecting North-West Russia with Germany through the Baltic States and Poland. North-West Russia plays important role not only in Russian logistics, but also wider European markets as in container sea ports handling is approx. 2.5 mill. TEU p.a. and handling volume in all terminals is above 190 million tons p.a. The whole transportation logistics sector is shortly described as an operational environment for railways – this is done through technical and economic angles. Transportation development is always going in line with economics of the country, so the analysis on economical development is also presented. Logistics integration of the country is strongly influenced by its engagement in the international trade. Although, raw material handling at sea ports and container transports (imports) are blossoming, domestic transportation market is barely growing (in long-term perspective). Thus, recent entrance of Russia into World Trade Organization (WTO) is analyzed theme in this research, as the WTO is an important regulator of the foreign trade and enabler of volume growth in foreign trade related transportation logistics. However, WTO membership can influence negatively the development of Russia’s own industry and its volumes (these have been uncompetitive in global markets for decades). Data gathering in empirical part was accomplished by semi-structured case study interviews among North-West Russian logistics sector actors (private). These were conducted during years 2012-2013, and research compiles findings out of ten case company interviews. Although, there was no sea port involved in the study, most of the interviewed companies relied in European Logistics within significant parts in short sea shipping and truck combined transportation chains (in Russian part also using railways). As the results of the study, it could be concluded that Rail Baltica is seen as possible transport corridor in most of the interviewed companies, if there is enough cargo available. However, interviewees are a bit sceptical, because major and large-scale infrastructural improvements are needed. Delivery time, frequency and price level are three main factors influencing the attractiveness of Rail Baltica route. Price level is the most important feature, but if RB can offer other advantages such as higher frequency, shorter lead times or more developed set of value-added services, then some flexibility is possible for the price level. Environmental issues are not the main criteria of today, but are recognized and discussed among customers. Great uncertainty exists among respondents e.g. on forthcoming sulphur oxide ban on Baltic Sea shipping (whether or not it is going to be implemented in Russia). Rather surprisingly, transportation routes to Eastern Europe and Mediterranean area are having higher value and price space than those to Germany/Central Europe. Border crossing operations (traction monopoly at rails and customs), gauge widths as well as unclear decision-making processes (in Russia), are named as hindering factors. Performance standards for European connected logistics among Russian logistics sector representatives are less demanding as compared to neighbourhood countries belonging to EU.

Syntyykö Suomeen puulaaksoja - Suomen puutuoteteollisuuden pk-yritysten tila ja tulevaisuus

Metsäteollisuus on tullut Suomeen ulkomaisen pääoman ja tietotaidon avulla vajaat kaksisataa vuotta sitten. Se on toiminut melkein koko jatkosodan jälkeisen ajan suojatussa ympäristössä ja ulkomaisesta kilpailusta riippumattomassa toimintaympäristössä. Kuten Porter ja muut ovat todistaneet, tällainen toimintaympäristö ei kehitä kansainvälisesti kilpailukykyistä teollisuutta globaaleilla markkinoilla. Liittyminen Euroopan unioniin ja sittemmin Euroopan rahaliittoon saattoi puunjalostusteollisuuden täysin uudenlaiseen kilpailutilanteeseen. Sama tapahtui myös alan pk-yrityksille, jotka olivat joutuneet toimimaan heikosti kilpailluilla raaka-ainemarkkinoilla. Tutkimus on tulevaisuudentutkimus, jossa tutkimusongelmia lähestytään kolmen teorian avulla. Porterin klusteriteoria tarjoaa mahdollisuuden arvioida metsäteollisuutta sekä kokonaisuutena että toimivana monimuotoisena organisaationa, jossa kustannukset ja hinta muodostuvat arvoketjun toimijoiden osakustannuksista. Bionomiateoria eli darvinistinen talousteoria testaa suomalaisen puunjalostusteollisuuden pk-yritysten kilpailukykyä ja paineita hakeutua edullisemmille toiminta- alueille. Evoluutioteoria tarkastelee sukupolvenvaihdoksen problematiikkaa. Sukupolvenvaihdoksen onnistuminen muodostuu puutoimialan elämän ja kuoleman kysymykseksi. Tämä on etenkin pk-yrityksiä kohtaava ongelma. Asiaa selvitettiin Mauno Rintalan suorittamalla kyselytutkimuksella Puuteollisuusyrittäjien jäsenistön keskuudessa. Ongelma johtuu suurista sodan jälkeen syntyneistä ikäluokista. Nämä vuosina 1945– 50 syntyneet ovat siirtymässä eläkkeelle vuosien 2005 ja 2015 välillä. Kyseisissä ikäluokissa yritystiheys on noin kaksi kertaa suurempi kuin sen jälkeisissä ikäluokissa. Suoritetun kyselyn sekä muiden suomalaisten ja kansainvälisten tutkimusten perusteella näyttää siltä, että eläkkeelle siirryttäessä vain noin 30 %:lla yrityksistä on jatkaja tiedossa suvusta tai lähipiiristä. Tämä merkitsee sitä, että 70 % eläköityvän ikäluokan omistamista yrityksistä poistuu pysyvästi markkinoilta. Suomessa poistuma merkitsee noin 40 % koko yritysvarannosta eli noin 80 000 yritystä. Tilastot toimivien yritysten määrästä ovat kuitenkin hyvin ristiriitaisia, joten todellista määrää on mahdoton arvioida. Noin suuren määrän poistuminen markkinoilta uhkaa jo hyvinvointivaltion perusrakenteita. Tutkimustulos edellyttää nopeita toimenpiteitä teollisten pkyritysten pelastamiseksi ja säilyttämiseksi Suomessa. Sukupolvenvaihdoksen onnistuminen on tässä prosessissa ensiarvoisessa asemassa. Kaikkien edellä mainittujen yritysten poistuminen markkinoilta edellyttäisi noin 400 000 uuden yrityksen perustamista, koska ainoastaan noin 20 % yrityksistä selviää ensimmäiset kolme vuotta. Tutkimukseen perustuen esitetään prosessimalli sukupolvenvaihdoksen suorittamiseksi. Suomen tärkeimmissä kilpailijamaissa valtioiden metsäomistus on määräävässä asemassa. Meillä metsät ovat yksityisessä omistuksessa ja vain pieni osa valtion omistuksessa. Puumarkkinat toimivat markkinatalouden ehdoilla ilman valtion ohjausta. Ongelmaksi on kehittymässä puun saanti. Metsänomistus on sukupolvien myötä hajaantunut hyvin pieniksi metsälöiksi. Nykyiset metsänomistajat asuvat kaupungeissa ja ovat pääosin palkkatyössä. He eivät ole samalla tavoin riippuvaisia puutuloista kuin heidän esi-isänsä. Metsäverotuksen uudistuminen lisää puun saannin epävarmuutta. Se on muuttumassa pinta-alaverotuksesta puun myynnin verotukseen. Puun myynti on vilkasta ennen järjestelmien vaihtumista ja vähäisempää sen jälkeen. Myös näitä ongelmia on pyritty ratkomaan uudenlaisen metsänomistusmallin avulla. Puuteollisuus on hyvin vanha teollisuudenala. Raaka-aine muodostaa määräävän osan kustannuksista. Muutokset ovat hitaita ja todelliset innovaatiot pitkäkestoisia. Uusia innovaatioita tapahtuu harvoin. Kannattavuutta parannetaan tuoteprosessien ja arvoketjujen kehittämisen kautta. Yhteiskunnan osuus alan kehittämisessä ja säilyttämisessä on ratkaiseva. Asioiden moninaisuus tekee tutkimuksen vaikeaksi, mutta sitäkin tärkeämmäksi kansantalouden kannalta. Tällaisissa suurissa murroksissa korostuu kaikkien päättävien tahojen henkinen valmius ja tahto tehdä oikeita ratkaisuja oikeaan aikaan.

Mäskin sisältämän ligniinin modifiointi PCD-hapetuksella

Teoriaosassa tutkittiin mäskin muodostumista oluentuotantoprosessissa, ligniiniä ja sen pilkkoutumista hapetuksella, eri kehittyneitä hapetusmenetelmiä ja hapetuksella saatavia potentiaalisia pääkomponentteja. Kehittyneissä hapetusmenetelmissä keskityttiin pääasiassa pulssitettuun koronapurkaukseen perustuvaan PCD-menetelmään (Pulsed Corona Discharge). Tutkittavana pääkomponenttina toimi glyoksyylihappo. Työn kokeellisessa osassa tutkittiin mäskistä erotetun ligniinin pilkkoutumista PCD-hapetuksella. Tässä menetelmässä hapetus perustuu sähköpurkauksen aikana syntyvien hydroksyyliradikaalien ja otsonin muodostumiseen, jotka voivat toimia hapettimina. Kokeissa käytettiin oluentuotannosta saatua mäskiä, josta ligniiniä liuotettiin natriumhydroksidi-vesi-liuoksen avulla uuttamalla.. Tämän jälkeen liuosta käsiteltiin PCD laitteistossa. PCD-käsiteltyä tuotetta analysoitiin mittaamalla ligniinin ja aldehydien pitoisuudet siitä spektrofotometrin avulla. Työn tarkoituksena on tutkia PCD hapetusmenetelmän soveltuvuutta mäskin sisältämän ligniinin muokkaamiseen siten, että siitä syntyvää tuotetta voitaisiin käyttää jossakin muussa sovelluksessa, kuten esimerkiksi lääkkeiden raaka-aineena lääketeollisuudessa. PCD hapetusmenetelmä on koronasähköpurkauksiin perustuva laite, jota käytetään pääasiassa vedenpuhdistuksessa hajoittamaan haitallisia orgaanisia yhdisteitä. Tämän työn perusteella ligniiniä hajosi, aldehydejä muodostui ja hapetusnäytteiden pH laski hapetusajan kasvaessa. Tämä viittasi vahvasti glyoksyylihapon muodostumiseen PCD-laitteistossa.

Fast pyrolysis in circulating fluidized bed: feasibility study

Today the limitedness of fossil fuel resources is clearly realized. For this reason there is a strong focus throughout the world on shifting from fossil fuel based energy system to biofuel based energy system. In this respect Finland with its proven excellent forestry capabilities has a great potential to accomplish this goal. It is regarded that one of the most efficient ways of wood biomass utilization is to use it as a feedstock for fast pyrolysis process. By means of this process solid biomass is converted into liquid fuel called bio-oil which can be burnt at power plants, used for hydrogen generation through a catalytic steam reforming process and as a source of valuable chemical compounds. Nowadays different configurations of this process have found their applications in several pilot plants worldwide. However the circulating fluidized bed configuration is regarded as the one with the highest potential to be commercialized. In the current Master’s Thesis a feasibility study of circulating fluidized bed fast pyrolysis process utilizing Scots pine logs as a raw material was conducted. The production capacity of the process is 100 000 tonne/year of bio-oil. The feasibility study is divided into two phases: a process design phase and economic feasibility analysis phase. The process design phase consists of mass and heat balance calculations, equipment sizing, estimation of pressure drops in the pipelines and development of plant layout. This phase resulted in creation of process flow diagrams, equipment list and Microsoft Excel spreadsheet that calculates the process mass and heat balances depending on the bio-oil production capacity which can be set by a user. These documents are presented in the current report as appendices. In the economic feasibility analysis phase there were at first calculated investment and operating costs of the process. Then using these costs there was calculated the price of bio-oil which is required to reach the values of internal rate of return of 5%, 10%, 20%, 30%, 40%, and 50%.

The pH-dependent phase distribution of wood pitch components in papermaking processes

Wood contains only a very small amount of lipophilic extractives, commonly known as wood pitch. The pitch is known to cause severe problems in papermaking processes. The amount of pitch in process waters can be decreased by seasoning of the raw material prior to pulping, pulp washing, removal of pitch by flotation, adsorption of pitch onto various mineral surfaces, and retention of pitch to the fibre material by cationic polymers. The aim of this study was to determine the influence of pH on some of the methods used for pitch control. Experiments were performed using laboratory-made wood pitch emulsions with varying pH, salt concentration, hemicellulose concentration and pitch composition. These emulsions were used to study the phase distribution of resin and fatty acids, the colloidal stability of pitch with and without steric stabilisation by galactoglucomannans, and the interactions between wood pitch and mineral particles. Purification of unbleached and peroxidebleached mill process water was performed by froth flotation in combination with a foaming agent. The distribution of resin and fatty acids (RFAs) between colloidal pitch droplets and the water phase was very dependent on pH. At pH 3, almost all of the RFAs were attached to the pitch droplets, while increasing the pH led to increasing concentration of dissolved RFAs in the water phase. The presence of salt shifted the release of RFAs towards higher pH, while lower ratio of neutral pitch in the emulsion resulted in release of RFAs at lower pH. It was also seen that the dissolution and adsorption of RFAs at sudden pHchanges takes place very quickly. Colloidal pitch was more stable against electrolyte-induced aggregation at higher pH, due to its higher anionic charge. The concentration of cationic polymers needed to aggregate colloidal pitch also increased with increasing pH. The surface characteristics of solid particles, such as amount of charged groups, were very important for understanding their interactions with colloidal wood pitch. Water-soluble galactoglucomannans stabilised the colloidal pitch sterically against aggregation, but could not completely prevent interactions between wood pitch and hydrophilic particles. Froth flotation of unbleached and peroxidebleached process water showed that the pitch could be removed more effectively and selectively at low pH, compared to at neutral pH. The pitch was removed more effectively, using lower concentrations of foaming agent, from peroxide-bleached water than from unbleached water. The results show that pH has a major impact on various pulping and papermaking processes. It determines the anionic charge of the colloidal pitch and the solubility of certain pitch components. Because of this, the pH influences the effectiveness of pitch retention and removal of pitch. The results indicate that pitch problems could be diminished by acknowledging the importance of pH in various papermaking processes.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.

Biohiilen tuotannon toimintaedellytykset Parikkalassa

Suomessa on sitouduttu kansainvälisiin päästövähennystavoitteisiin ja uusiutuvan ener-gian osuuden kasvattamiseen. Biohiili on erinomainen polttoainevaihtoehto kivihiili-voimalaitoksissa, sillä sitä voidaan käyttää suurellakin seososuudella ilman merkittäviä rakenteellisia muutoksia polttoaineen syöttölaitteistoihin tai kattilaan. Biohiiltä voidaan käyttää myös metallurgiassa pelkistimenä, maanparannusaineena ja hiilinieluna. Biohiilen raaka-aineena toimii energia- ja kuitupuuhake. Parikkalan lähialueella on hyödyn-nettävissä olevaa teknis-taloudellista metsäenergiapotentiaalia keskisuuren biojalostamon perustamista varten. Biohiilen teoreettinen markkinapotentiaali on valtava, mutta sen taloudelliset kannattavuusnäkymät ovat heikot nykyhintatasolla. Biohiilen kilpailukykyä heikentävät kivihiilen ja päästöoikeuksien alhaiset hinnat ja biohiilen korkeat tuotantokustannukset. Biohiilimarkkinoiden kehittymistä jarruttaa myös olemassa olevan tuotannon puute. Biohiilen käyttöönotto edellyttäisi kansainvälisiä tukitoimia tai kivihiilen hinnan kasvua.