Effect of additives, precursors and process conditions on particle morphology

The objective of the thesis was to develop methods to manufacture and control calcium carbonate crystal nucleation and growth in precipitation process. The work consists of experimental part and literature part that addresses theory of nucleation, crystallization and precipitation. In the experimental part calcium carbonate was precipitated using carbonization reaction. Precipitation was carried out in presence of known morphology controlling agents (anionic polymers and sodium silicate) and by using different operation conditions. Formed material was characterized using SEM images, and its thermal stability was assessed. This work demonstrates that carbon dioxide feeding rate and concentrations of calcium hydroxide and additives can be used to control size, shape and amount of precipitating calcium carbonate.

Hitsattavan konstruktion laadun ja rakenteen kehittäminen lyöntipaalutuskoneessa

Työn tavoitteena oli Junttan Oy:n valmistaman lyöntipaalutuskoneeseen kuuluvan tärkeän konstruktion, peruskeilin, laadun ja rakenteen kehittäminen. Työ tehtiin osana Tekesin ja usean yrityksen rahoittamaa HitNet-projektia (Hitsaavan teollisuuden hankintatoimen ja toimitusketjun tehostaminen). Peruskeiliä tutkittiin seuraamalla sen valmistusta Junttan Oy:n omassa tuotannossa sekä alihankintayrityksissä. Ongelmana peruskeilin suunnittelussa ja valmistuksessa olivat hyvin tarkat toleranssirajat sen liukupinnoille. Suurimmat ongelmat syntyivät hitsaamisen tuoman suuren lämmöntuonnin aiheuttamien muodonmuutosten ja särmäyksestä johtuvan takaisinjouston yhteydessä. Näihin ongelmiin pyrittiin kehittämään ratkaisuja peruskeilin rakennetta muuttamalla, Total Welding Management -laatutyökalua hyödyntämällä sekä hitsaustoimintaa ja särmäystä kehittämällä. Peruskeilin suunnittelussa ja valmistuksessa havaittujen ongelmien perusteella kehitettiin useita ratkaisuja, joista yksi otettiin käyttöön ja siitä valmistetaan prototyyppi Junttan Oy:n omassa tuotannossa. Uuden mallin valmistuessa päätetään tuleeko siitä korvaaja edeltäjälleen vai testataanko vielä muita kehitysideoita.

Quality, Productivity and Economy in Welding Manufacturing - Case Study: West Africa

This thesis studies quality, productivity and economy in welding manufacturing in West African states such as Ghana, Nigeria and Cameroon. The study consists of two parts: the first part, which forms the theoretical background, reviews relevant literature concerning the metal and welding industries, and measurement of welding quality, productivity and economy. The second part, which is the empirical part, aims to identify activities in the metal manufacturing industries where welding is extensively used and to determine the extent of welding quality, productivity and economy measurements in companies operating in the metal manufacturing industries. Additionally, the thesis aims to identify challenges that companies face and to assess the feasibility of creating a network to address these issues. The research methods used in the empirical part are the case study (qualitative) method and the survey (quantitative) method. However, the case study method was used to elicit information from companies in Ghana, while the survey method was used to elicit information from companies in Nigeria and Cameroon. The study considers important areas that contribute to creating awareness and understanding of the current situation of the welding industry in West Africa. These areas include the metal manufacturing industrial sector, metal products manufactured, metal production and manufacturing systems deployed, welding quality, productivity and economy measurement systems utilized, equipment and materials on the markets, general challenges facing companies in welding operations, welding technology programs and research in local universities, and SWOT analysis of the various West African states. The notable findings indicate that majority of the companies operate in the constructionindustrial sector. Also, majority of the companies are project manufacturing oriented, thus provide services to customers operating in the growing industries such as the oil and gas, mining, food and the energy industry. In addition, only few companies are certified under standards such as ISO 9001, ISO 3834, and OHSAS 18001. More so, majority of the companies employ manual welding technique, and shielded metal arc welding (SMAW) as the commonly used welding process. Finally, welder salary is about € 300 / month as of June 2013 and the average operations turnover of medium to large companies is about € 5 million / year as at 2012. Based on analysis of the results of the study, it is noted that while welding activities are growing, the availability of cheap labor, the need for company and welder qualification and certification, and the need to manufacture innovative products through developmental projects (transfer of welding expertise and technology) remain as untapped opportunities in the welding industry in the West African states. The study serves as a solid platform for further research and concludes with several recommendations for development of the West African welding industry.

PDM system functions and utilizations analysis to improve efficiency of sheet metal product design and manufacturing

This study will concentrate on Product Data Management (PDM) systems, and sheet metal design features and classification. In this thesis, PDM is seen as an individual system which handles all product-related data and information. The meaning of relevant data is to take the manufacturing process further with fewer errors. The features of sheet metals are giving more information and value to the designed models. The possibility of implementing PDM and sheet metal features recognition are the core of this study. Their integration should make the design process faster and manufacturing-friendly products easier to design. The triangulation method is the basis for this research. The sections of this triangle are: scientific literature review, interview using the Delphi method and the author’s experience and observations. The main key findings of this study are: (1) the area of focus in triangle (the triangle of three different point of views: business, information exchange and technical) depends on the person’s background and their role in the company, (2) the classification in the PDM system (and also in the CAD system) should be done using the materials, tools and machines that are in use in the company and (3) the design process has to be more effective because of the increase of industrial production, sheet metal blank production and the designer’s time spent on actual design and (4) because Design For Manufacture (DFM) integration can be done with CAD-programs, DFM integration with the PDM system should also be possible.

European luxury brands made in China: the effect of low-cost country manufacturing on brand image and purchase decisions

European luxury brands have an image of manufacturing their products in the same country where the brands originate. However, in the past years many luxury brands have shifted their manufacturing to countries outside Europe. China is now a common manufacturing country for European luxury brands despite the country’s poor image as a manufacturer. Chinese manufacturing is often associated with bad quality, bad labour conditions, mass production, and counterfeits. The image of China does not quite match the image luxury brands enjoy including characteristics such as high end quality, craftsmanship, details, design, or premium price. A negatively perceived country-of-manufacture may have an effect on a brand’s image and consumers’ purchase decisions. This thesis is focused on European luxury brands manufacturing in China, and how this effects the brand image and purchase decisions among luxury consumers. The empirical part of this thesis is based on focus group research, which is a popular method in the field of qualitative research. The main focus group is female luxury consumers in Finland. This main group has been divided into three categories: 1) the university students, 2) the young career women, 3) the experienced luxury consumers. This categorization has been done based on their different stages in luxury consumption. All in all, the empirical research consisted of 11 interviews and 29 participants. The main contribution of this thesis was that there is a difference between the opinions of the younger groups (university students and young career women) and the experienced luxury consumers when discussing the effect of country-of-manufacture on brand image and purchase decisions of luxury brands. The younger participants thought that manufacturing luxury products in China might affect the brand image, but their purchase decisions would not be that much affected by the country-of-origin. The experienced luxury consumers had quite a different view on the country-of-origin of luxury brands – they found it an important decisive factor prior making purchases. The majority of experienced luxury consumers would not buy luxury products made in China, and they would always check where these products are made in.

Chromium mass balance in sodium chlorate process

Kuudenarvoista kromia käytetään natriumkloraatin valmistuksessa prosessin tuotantotehokkuuden ja turvallisuuden parantamiseksi. Kromia kuitenkin poistuu prosessista muutamaa reittiä pitkin. Koska kuuudenarvoisella kromilla on syöpää aiheuttavia, mutageenisiä sekä lisääntymiselle myrkyllisiä ominaisuuksia, olisi tärkeää ymmärtää, miten kromi kulkeutuu prosessin eri osiin, ja kuinka paljon sitä poistuu prosessista. Tämä on tärkeää, jotta osataan hallita kromin käytöstä aiheutuvat riskit, sekä toisaalta myös tehostaa kromin käyttöä prosessissa. Työn tarkoituksena oli tuottaa tietoa kromin käytöstä natriumkloraattiprosessissa. Työssä tutkittiin kromitasetta prosessin keskeisimmissä yksikköoperaatioissa. Myös kromin saostumista katodien pinnalle arvioitiin määrällisesti. Eri prosessinäytteistä tutkittiin lisäksi kromin hapetusasteita. Edellä mainittuja tutkimuskohteita varten määritettiin prosessinäytteiden kromipitoisuus. Eri prosessioperaatioille suoritettiin lisäksi taselaskelmat. Työn tuloksena esitettiin kromitase sekä yksikköoperaatioille että koko prosessille. Erinäisten epätarkkuustekijöiden vuoksi tasetta ei kuitenkaan pystytty määrittämään halutulla tarkkuudella, ja siksi työssä esitettyä tasetta voidaan pitää vain suuntaa antavana laskelmana. Katodien pinnalle saostunutta kromin määrää pidettiin kuitenkin oikean suuruusluokan tuloksena. Prosessinäytteiden hapetusasteita ei voitu arvioida, sillä saadut kokonaiskromitulokset eivät olleet täysin luotettavia. Huolimatta tulosten epätarkkuudesta, työ tuotti tärkeää tietoa prosessin toiminnasta kromin suhteen. Työtä voidaan hyödyntää jatkossa monin tavoin prosessin kromitaseen seurannassa.

Laserhitsattavan tuotteen suunnittelu

Tässä työssä tarkastellaan laserhitsattavan tuotteen suunnittelua ja sen tuotekehitykseen liittyviä tekijöitä. Tuotteen suunnittelua käsitellään valmistuksellisesta näkökulmasta, eli siitä, kuinka tuotteen suunnittelussa voidaan ottaa huomioon tuotteen valmistus- ja kokoonpanoystävällisyys. Laserhitsattavan tuotteen suunnittelua käsitellään myös tuotteen ominaisuuksien kannalta, eli kuinka lopullisesta tuotteesta saadaan mahdollisimman laadukas ja kilpailukykyinen. Suomen kaarihitsausosaaminen on kansainvälisesti korkealuokkaista, mutta laserhitsaus eroaa perinteisistä kaarihitsausprosesseista paljon. Kun laserilla hitsattavaa tuotetta suunnitellaan, ovat menetelmäkohtaiset suunnittelusäännöt erilaiset kuin kaarihitsauksessa. Laserhitsaus vaatii teknisesti pajalta enemmän, mutta se myös avaa uusia ovia tuotesuunnittelulle ja mahdollistaa tuotteita, jotka olisivat perinteisillä menetelmillä hankalia tai mahdottomia valmistaa. Oikein käyttöönotettuna laserhitsauksella voidaan päästä matalampiin valmistuskustannuksiin. Kustannustehokkaaseen tuotantoon päästäkseen täytyy kuitenkin ymmärtää tuotteen kustannusrakenne. Työn lopussa tarkastellaan ja vertaillaan perinteisen ja laserhitsatun tuotteen kustannuksia ja kustannusrakennetta.

α-Pinene oxide and verbenol oxide isomerizations over heterogeneous catalysts

Terpenes are a valuable natural resource for the production of fine chemicals. Turpentine, obtained from biomass and also as a side product of softwood industry, is rich in monoterpenes such as α-pinene and β-pinene, which are widely used as raw materials in the synthesis of flavors, fragrances and pharmaceutical compounds. The rearrangement of their epoxides has been thoroughly studied in recent years, as a method to obtain compounds which are further used in the fine chemical industry. The industrially most desired products of α-pinene oxide isomerization are campholenic aldehyde and trans-carveol. Campholenic aldehyde is an intermediate for the manufacture of sandalwood-like fragrances such as santalol. Trans-carveol is an expensive constituent of the Valencia orange essence oil used in perfume bases and food flavor composition. Furthermore it has been found to exhibit chemoprevention of mammary carcinogenesis. A wide range of iron and ceria supported catalysts were prepared, characterized and tested for α-pinene oxide isomerization in order to selective synthesis of above mentioned products. The highest catalytic activity in the preparation of campholenic aldehyde over iron modified catalysts using toluene as a solvent at 70 °C (total conversion of α-pinene oxide with a selectivity of 66 % to the desired aldehyde) was achieved in the presence of Fe-MCM-41. Furthermore, Fe-MCM-41 catalyst was successfully regenerated without deterioration of catalytic activity and selectivity. The most active catalysts in the synthesis of trans-carveol from α-pinene oxide over iron and ceria modified catalysts in N,N-dimethylacetamide as a solvent at 140 °C (total conversion of α-pinene oxide with selectivity 43 % to trans-carveol) were Fe-Beta-300 and Ce-Si-MCM-41. These catalysts were further tested for an analogous reaction, namely verbenol oxide isomerization. Verbenone is another natural organic compound which can be found in a variety of plants or synthesized by allylic oxidation of α-pinene. An interesting product which is synthesized from verbenone is (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol. It has been discovered that this diol possesses potent anti-Parkinson activity. The most effective way leading to desired diol starts from verbenone and includes three stages: epoxidation of verbenone to verbenone oxide, reduction of verbenone oxide and subsequent isomerization of obtained verbenol oxide, which is analogous to isomerization of α-pinene oxide. In the research focused on the last step of these synthesis, high selectivity (82 %) to desired diol was achieved in the isomerization of verbenol oxide at a conversion level of 96 % in N,N-dimethylacetamide at 140 °C using iron modified zeolite, Fe-Beta-300. This reaction displayed surprisingly high selectivity, which has not been achieved yet. The possibility of the reuse of heterogeneous catalysts without activity loss was demonstrated.

Simulation of wind powered hydraulic heating system

The objective of this master’s thesis was to design and simulate a wind powered hydraulic heating system that can operate independently in remote places where the use of electricity is not possible. Components for the system were to be selected in such a way that the conditions for manufacture, use and economic viability are the as good as possible. Savonius rotor was chosen for wind turbine, due to its low cut in speed and robust design. Savonius rotor produces kinetic energy in wide wind speed range and it can withstand high wind gusts. Radial piston pump was chosen for the flow source of the hydraulic heater. Pump type was selected due to its characteristics in low rotation speeds and high efficiency. Volume flow from the pump is passed through the throttle orifice. Pressure drop over the orifice causes the hydraulic oil to heat up and, thus, creating thermal energy. Thermal energy in the oil is led to radiator where it conducts heat to the environment. The hydraulic heating system was simulated. For this purpose a mathematical models of chosen components were created. In simulation wind data gathered by Finnish meteorological institute for 167 hours was used as input. The highest produced power was achieved by changing the orifice diameter so that the rotor tip speed ratio follows the power curve. This is not possible to achieve without using electricity. Thus, for the orifice diameter only one, the optimal value was defined. Results from the simulation were compared with investment calculations. Different parameters effecting the investment profitability were altered in sensitivity analyses in order to define the points of investment profitability. Investment was found to be profitable only with high average wind speeds.

Katsaus lisäävän valmistuksen (aka 3D-tulostus) mahdollisuuksiin ja kustannuksiin metallisten tuotteiden valmistuksessa: Case jauhepetitekniikka

Suurelle yleisölle lisäävä valmistustekniikka eli ns. 3D-tulostustekniikka näyttäytyy lehtien otsikoissa ja artikkeleissa esiin pulpahtavana ”muotiaiheena”, mutta sekä muovien 3D-tulostustekniikka että metallienkin vastaava valmistustekniikka on ollut olemassa maailmalla ja Suomessa 80-luvun puolivälistä alkaen. Yhdysvalloissa ja Saksassa tekniikkaa käytetään valmistavassa teollisuudessa toiminnallisten osien tuotannossa. Esimerkiksi lentokoneen suihkumoottorien osia ja lääketieteellisiä välineitä tehdään metallijauheesta lisäävän valmistuksen avulla. Itse asiassa eräs menetelmä metalliesineiden valmistamiseksi lasersäteen avulla keksittiin Suomessa ja sitä myös kehiteltiin täällä, mutta teollisuudenala lähti aikanaan nousuun Saksassa. Lisäävä valmistus on tällä hetkellä maailmanlaajuisesti eräs kiinnostavista tuotantotekniikoista, jonka uskotaan muuttavan monia asioita tuotteiden suunnittelussa, toiminnoissa ja valmistuksessa. Tämä tekniikka ei kiinnosta pelkästään valmistavaa teollisuutta, vaan tietotekniikan, lääketieteen, koruvalmistuksen ja muotoilun osaajat sekä uusien liiketoimintamallien kehittäjät ja logistiikka operaattorit ovat teknologiasta kiinnostuneita. Suomelle 3D-tulostustekniikka on suuri mahdollisuus, sillä maassamme on vahva teollinen tieto- ja viestintätekniikkaosaaminen sekä lisäksi olemme maassamme erikoistuneet varsin vaativien teollisiin laitteiden valmistukseen. Eräät suurimmista mahdollisuuksista tällä tekniikalla ovat toimitusketjuihin liittyvät muutokset. Uutta on, että pienetkin yritykset ja organisaatiot voivat soveltaa tätä tekniikkaa valmistuksessa ja jopa kehitellä täysin uusia tuotteita. On myös arvioitu, että lisäävän valmistuksen merkitys valmistustapoihin ja toimitusketjuihin voi olla suurempi kuin koskaan aikaisemmin minkään teknologisen uudistuksen kohdalla. Lisäävästä valmistuksesta usein puhutaankin kolmantena teollisena vallankumouksena juuri tämän takia. 3D-tulostuksen kustannuksia tarkasteltaessa on tärkeätä huomata että vain sulatetun jauheen määrä ratkaisee, ei käytettävän geometrian monimutkaisuus. Tämä erottaa perinteisen ja lisäävän valmistuksen toisistaan. Perinteisesti kappaleen keventäminen on maksanut ”ylimääräistä”, kun taas lisäävässä valmistuksessa kappaleen keveys on jopa kustannusta alentava tekijä. Valmistettavan kappaleen korkeus on yksi kriittisimpiä kustannuksiin vaikuttavia tekijöitä. Tämän vuoksi useamman kappaleen valmistus yhdellä kertaa parantaa kannattavuutta huomattavasti. Samalla kertaa voi ja itse asiassa kannattaakin valmistaa keskenään erilaisia kappaleita. Perinteiset valmistustavat sen sijaan ovat nykyajan vaatimuksille liian hitaita; ne joustavat huonosti, kun kyseessä on pienet, asiakaslähtöiset erät. Trendi on globaalisti kohden yksilöllisiä asiakaslähtöisiä tuotteita, jolloin myös valmistustekniikoiden on oltava joustavia pysyäkseen näiden vaatimusten perässä. Lisäävä valmistus sopii erityisesti hyvin piensarjatuotantoon. Suuremmissa valmistuserissä kuitenkin perinteiset tekniikat ovat kustannustehokkaampia.

Konepajan hitsaustuotannon kehittäminen kattavien laatuvaatimusten mukaiseksi

TIIVISTELMÄ Lappeenrannan teknillinen yliopisto Konetekniikan koulutusohjelma Voitto Kettunen Konepajan hitsaustuotannon kehittäminen kattavien laatuvaatimusten mukaiseksi Diplomityö 2015 167 sivua, 39 kuvaa, 26 taulukkoa ja 3 liitettä Tarkastajat: Professori Jukka Martikainen DI Pertti Kaarre Hakusanat: hitsaus, hitsauksen laatu, konepajan laadunhallinta, kattavat laatuvaatimukset, ISO 9001, ISO 3834, EN 1090 Keywords: welding, quality of welding, engineering workshop quality management, comprehensive quality requirements, ISO 9001, ISO 3834, EN 1090 Hitsaamalla liitetyt teräksiset rakenteet muodostavat ylivoimaisesti suurimman osan konepajatuotannosta. Niihin kuuluu esimerkiksi ajoneuvoja, koneita, laitteita, säiliöitä, siiloja, siltoja, mastoja, piippuja, tukirakenteita ja rakennusten runkoja. Tämän diplomityön tavoitteena on kehittää konepajan laadunhallinta sellaiseksi, että se mahdollistaa kattavien laatuvaatimusten täyttämisen hitsaustuotannossa. Laatuvaatimusten täyttämiseen pyritään käyttämällä hitsaustoimintojen standardia EN ISO 3834-2 sekä kantavien teräsrakenteiden standardeja EN 1090-1 ja EN 1090-2. Teräsrakenteiden suunnittelua ohjaa EN 1993 ja niiden toiminnallisia ominaisuuksia tuotestandardit, kuten terässavupiippu- ja säiliöstandardit. Kantavien teräsrakenteiden suunnittelua ja tuotantoa ohjaa myös seuraamusluokan CC, käyttöluokan SC ja tuotantoluokan PC kautta määräytyvä toteutusluokka EXC. Aikaisempaa enemmän tullaan panostamaan esimerkiksi asiakirjojen sähköiseen hallintaan, raaka-aineiden jäljitettävyyteen tuotteeseen, särmien ja kulmien muotoiluun, pintojen käsittelyyn, hitsien tarkastukseen, hitsaushenkilöstön pätevyyteen ja hitsaustuotannon tehokkuuteen. Saarijärven Säiliövalmiste Oy:n hitsauksen laadunhallinta sertifioitiin standardin ISO 3834-2 mukaan ja kantavien teräsrakenteiden FPC-järjestelmä standardisarjaa EN 1090 noudattaen. Samalla tehtiin päivitys laadunhallintajärjestelmään ISO 9001. Toteutus, joka tehtiin sovitussa aikataulussa, haastaa jokaisen toimijan konepajassa toiminnan, tuotannon ja tuotteiden laadun kehittämiseen uusia käytänteitä ja menetelmiä soveltaen. Kehitystoimien tuloksena toiminta on selkeämpää, ennakoitavampaa ja hallitumpaa, mikä lisää yrityksen toiminnan tuottavuutta ja kannattavuutta. Sertifioidut laatujärjestelmät ovat myötävaikuttaneet tilausten lisääntymiseen yrityksen kaikkien tuotteiden osalta.

Energy and raw material consumption analysis of powder bed fusion: case study: CNC machining and laser additive manufacturing

Laser additive manufacturing (LAM), known also as 3D printing, is a powder bed fusion (PBF) type of additive manufacturing (AM) technology used to manufacture metal parts layer by layer by assist of laser beam. The development of the technology from building just prototype parts to functional parts is due to design flexibility. And also possibility to manufacture tailored and optimised components in terms of performance and strength to weight ratio of final parts. The study of energy and raw material consumption in LAM is essential as it might facilitate the adoption and usage of the technique in manufacturing industries. The objective this thesis was find the impact of LAM on environmental and economic aspects and to conduct life cycle inventory of CNC machining and LAM in terms of energy and raw material consumption at production phases. Literature overview in this thesis include sustainability issues in manufacturing industries with focus on environmental and economic aspects. Also life cycle assessment and its applicability in manufacturing industry were studied. UPLCI-CO2PE! Initiative was identified as mostly applied exiting methodology to conduct LCI analysis in discrete manufacturing process like LAM. Many of the reviewed literature had focused to PBF of polymeric material and only few had considered metallic materials. The studies that had included metallic materials had only measured input and output energy or materials of the process and compared to different AM systems without comparing to any competitive process. Neither did any include effect of process variation when building metallic parts with LAM. Experimental testing were carried out to make dissimilar samples with CNC machining and LAM in this thesis. Test samples were designed to include part complexity and weight reductions. PUMA 2500Y lathe machine was used in the CNC machining whereas a modified research machine representing EOSINT M-series was used for the LAM. The raw material used for making the test pieces were stainless steel 316L bar (CNC machined parts) and stainless steel 316L powder (LAM built parts). An analysis of power, time, and the energy consumed in each of the manufacturing processes on production phase showed that LAM utilises more energy than CNC machining. The high energy consumption was as result of duration of production. Energy consumption profiles in CNC machining showed fluctuations with high and low power ranges. LAM energy usage within specific mode (standby, heating, process, sawing) remained relatively constant through the production. CNC machining was limited in terms of manufacturing freedom as it was not possible to manufacture all the designed sample by machining. And the one which was possible was aided with large amount of material removed as waste. Planning phase in LAM was shorter than in CNC machining as the latter required many preparation steps. Specific energy consumption (SEC) were estimated in LAM based on the practical results and assumed platform utilisation. The estimated platform utilisation showed SEC could reduce when more parts were placed in one build than it was in with the empirical results in this thesis (six parts).

Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.

Intensification of hemicellulose hot-water extraction from spruce wood by parameter tuning

The growing population on earth along with diminishing fossil deposits and the climate change debate calls out for a better utilization of renewable, bio-based materials. In a biorefinery perspective, the renewable biomass is converted into many different products such as fuels, chemicals, and materials, quite similar to the petroleum refinery industry. Since forests cover about one third of the land surface on earth, ligno-cellulosic biomass is the most abundant renewable resource available. The natural first step in a biorefinery is separation and isolation of the different compounds the biomass is comprised of. The major components in wood are cellulose, hemicellulose, and lignin, all of which can be made into various end-products. Today, focus normally lies on utilizing only one component, e.g., the cellulose in the Kraft pulping process. It would be highly desirable to utilize all the different compounds, both from an economical and environmental point of view. The separation process should therefore be optimized. Hemicelluloses can partly be extracted with hot-water prior to pulping. Depending in the severity of the extraction, the hemicelluloses are degraded to various degrees. In order to be able to choose from a variety of different end-products, the hemicelluloses should be as intact as possible after the extraction. The main focus of this work has been on preserving the hemicellulose molar mass throughout the extraction at a high yield by actively controlling the extraction pH at the high temperatures used. Since it has not been possible to measure pH during an extraction due to the high temperatures, the extraction pH has remained a “black box”. Therefore, a high-temperature in-line pH measuring system was developed, validated, and tested for hot-water wood extractions. One crucial step in the measurements is calibration, therefore extensive efforts was put on developing a reliable calibration procedure. Initial extractions with wood showed that the actual extraction pH was ~0.35 pH units higher than previously believed. The measuring system was also equipped with a controller connected to a pump. With this addition it was possible to control the extraction to any desired pH set point. When the pH dropped below the set point, the controller started pumping in alkali and by that the desired set point was maintained very accurately. Analyses of the extracted hemicelluloses showed that less hemicelluloses were extracted at higher pH but with a higher molar-mass. Monomer formation could, at a certain pH level, be completely inhibited. Increasing the temperature, but maintaining a specific pH set point, would speed up the extraction without degrading the molar-mass of the hemicelluloses and thereby intensifying the extraction. The diffusion of the dissolved hemicelluloses from the wood particle is a major part of the extraction process. Therefore, a particle size study ranging from 0.5 mm wood particles to industrial size wood chips was conducted to investigate the internal mass transfer of the hemicelluloses. Unsurprisingly, it showed that hemicelluloses were extracted faster from smaller wood particles than larger although it did not seem to have a substantial effect on the average molar mass of the extracted hemicelluloses. However, smaller particle sizes require more energy to manufacture and thus increases the economic cost. Since bark comprises 10 – 15 % of a tree, it is important to also consider it in a biorefinery concept. Spruce inner and outer bark was hot-water extracted separately to investigate the possibility to isolate the bark hemicelluloses. It was showed that the bark hemicelluloses comprised mostly of pectic material and differed considerably from the wood hemicelluloses. The bark hemicelluloses, or pectins, could be extracted at lower temperatures than the wood hemicelluloses. A chemical characterization, done separately on inner and outer bark, showed that inner bark contained over 10 % stilbene glucosides that could be extracted already at 100 °C with aqueous acetone.

Recovery boilers - history and future

Recovery boilers are built all over the world. The roots of recovery technology are longer than the roots of recovery boilers. But it wasn’t until the invention of recovery boilers before the Second World War that the pulping technology was revolutionalized. This led to long development of essentially the same type of equipment, culminating into units that are largest biofuel boilers in the world. Early recovery technology concentrated on chemical recovery as chemicals cost money and if one could recycle these chemicals then the profitability of pulp manufacture would improve. For pulp mills the significance of electricity generation from the recovery boiler was for long secondary. The most important design criterion for the recovery boiler was a high availability. The electricity generation in recovery boiler process can be increased by elevated main steam pressure and temperature or by higher black liquor dry solids as well as improving its steam cycle. This has been done in the modern Scandinavian units.