West-Indische paskaert waer in de graden der breedde over wederzÿden van de middellÿn wassende so vergrooten dat die geproportioneert sÿn tegen hunne nevenstaende graden der lengde ..

Nimeke- ja tekijätiedot nimiönkehyksissä

West-Indische paskaert waer in de graden der breedde over wederzÿden van de middellÿn wassende so vergrooten dat die geproportioneert sÿn tegen hunne nevenstaende graden der lengde ...

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Oversiktskart over Nordpolarlandene fra Grönland i vest til Bering-Straedet i öst efter de nyeste kilder tilligemed Vegas kurs fra Jenisei til Östkap 1878-79

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Catalytic upgrading of biomass extractives to fine chemicals over supported ionic liquid catalysts (SILCAs)

Behovet av förnyelsebar energi ökar ständigt eftersom det finns en strävan att minska beroendet av fossila bränslen. Dessutom är tillgångar av fossila bränslen begränsade. Miljövänliga processer för bioraffinaderier erbjuder en stor möjlighet för produktion av energi, bränslen och kemikalier. Den finska och svenska skogsindustrin har en lång tradition i utnyttjandet av skogsbiomassor. Bioraffinaderier som integreras med pappers- och cellulosaindustrin kan frambringa både ekonomiska och ekologiska fördelar i framställning av traditionella och biobaserade produkter. I doktorsarbetet studerades omvandling av extraktivämnen till finkemikalier som kan användas t.ex. av läkemedelsindustrin. Extraktivämnen fås ur biomassa. I forskningsarbetet framställdes biobaserade finkemikalier med hjälp av katalysatorer som baserar sig på joniska vätskor. Biomassan består av cellulosa, hemicellulosa, lignin och extraktivämnen, vilka huvudsakligen är terpener, vaxer och fettsyror. Extraktivämen är vedens komponenter, som kan separeras ur vedmaterialet med hjälp av neutrala lösningsmedel. Joniska vätskekatalysatorer som var immobiliserade på fasta bärare utnyttjades för isomerisering av α,β-pinenoxider samt hydrogenering citral. Inverkan av joniska vätskor på katalysatorns aktivitet och reaktionernas produktfördelning undersöktes under varierande reaktionsbetingelser. Kinetiska modeller för pinenoxidens isomeriseringsreaktioner beskrev väl experimentellt upptäckta skillnader mellan olika katalysatorer. --------------------------------------------------- Uusiutuvan energian tarve on kasvussa, koska riippuvuutta fossiilisista polttoaineista pyritään vähentämään. Tämän lisäksi fossiilisten polttoaineiden varannot ovat rajalliset. Ympäristöystävälliset biojalostusprosessit ovat näin ollen suuri mahdollisuus energian, polttoaineiden ja kemikaalien tuotannossa. Suomen ja Ruotsin metsäteollisuudella on pitkät perinteet metsäbiomassojen hyödyntämisessä. Paperi- ja selluteollisuuden yhteyteen integroiduilla biojalostamoilla voidaan luoda taloudellisia ja ympäristöllisiä etuja sekä perinteisten että biopohjaisten tuotteiden valmistuksessa. Väitöstyössä on tutkittu biomassan uuteaineiden kemiallista muuntamista hienokemikaaleiksi, joita voidaan käyttää esimerkiksi lääkeaineteollisuudessa. Biopohjaisia hienokemikaaleja on valmistettu biomassan uuteaineista ionisiin nesteisiin perustuvilla katalyyteillä. Biomassa koostuu selluloosasta, hemiselluloosasta, ligniinistä sekä uuteaineista, jotka ovat pääosin terpeenejä, vahoja tai rasvahappoja. Uuteaineet ovat puun komponentteja, jotka voidaan erottaa puusta neutraalien liuottimien avulla. Kiinteän kantajan päälle immobilisoituja ionisia nestekatalyyttejä (Supported Ionic Liquid Catalyst) hyödynnettiin α,β-pineenioksidien isomerisointireaktioissa sekä sitraalin vedytysreaktioissa. Ionisten nesteiden vaikutusta katalyyttien aktiivisuuteen sekä reaktioiden tuotejakaumaan tutkittiin erilaisissa reaktio-olosuhteissa. Pineenioksidien isomerisointireaktioiden kineettiset mallit kuvasivat hyvin kokeellisesti todettuja katalyyttien eroavaisuuksia.

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.

Large-eddy simulation of wind flows over complex terrains for wind energy applications

Wind energy has obtained outstanding expectations due to risks of global warming and nuclear energy production plant accidents. Nowadays, wind farms are often constructed in areas of complex terrain. A potential wind farm location must have the site thoroughly surveyed and the wind climatology analyzed before installing any hardware. Therefore, modeling of Atmospheric Boundary Layer (ABL) flows over complex terrains containing, e.g. hills, forest, and lakes is of great interest in wind energy applications, as it can help in locating and optimizing the wind farms. Numerical modeling of wind flows using Computational Fluid Dynamics (CFD) has become a popular technique during the last few decades. Due to the inherent flow variability and large-scale unsteadiness typical in ABL flows in general and especially over complex terrains, the flow can be difficult to be predicted accurately enough by using the Reynolds-Averaged Navier-Stokes equations (RANS). Large- Eddy Simulation (LES) resolves the largest and thus most important turbulent eddies and models only the small-scale motions which are more universal than the large eddies and thus easier to model. Therefore, LES is expected to be more suitable for this kind of simulations although it is computationally more expensive than the RANS approach. With the fast development of computers and open-source CFD software during the recent years, the application of LES toward atmospheric flow is becoming increasingly common nowadays. The aim of the work is to simulate atmospheric flows over realistic and complex terrains by means of LES. Evaluation of potential in-land wind park locations will be the main application for these simulations. Development of the LES methodology to simulate the atmospheric flows over realistic terrains is reported in the thesis. The work also aims at validating the LES methodology at a real scale. In the thesis, LES are carried out for flow problems ranging from basic channel flows to real atmospheric flows over one of the most recent real-life complex terrain problems, the Bolund hill. All the simulations reported in the thesis are carried out using a new OpenFOAM® -based LES solver. The solver uses the 4th order time-accurate Runge-Kutta scheme and a fractional step method. Moreover, development of the LES methodology includes special attention to two boundary conditions: the upstream (inflow) and wall boundary conditions. The upstream boundary condition is generated by using the so-called recycling technique, in which the instantaneous flow properties are sampled on aplane downstream of the inlet and mapped back to the inlet at each time step. This technique develops the upstream boundary-layer flow together with the inflow turbulence without using any precursor simulation and thus within a single computational domain. The roughness of the terrain surface is modeled by implementing a new wall function into OpenFOAM® during the thesis work. Both, the recycling method and the newly implemented wall function, are validated for the channel flows at relatively high Reynolds number before applying them to the atmospheric flow applications. After validating the LES model over simple flows, the simulations are carried out for atmospheric boundary-layer flows over two types of hills: first, two-dimensional wind-tunnel hill profiles and second, the Bolund hill located in Roskilde Fjord, Denmark. For the twodimensional wind-tunnel hills, the study focuses on the overall flow behavior as a function of the hill slope. Moreover, the simulations are repeated using another wall function suitable for smooth surfaces, which already existed in OpenFOAM® , in order to study the sensitivity of the flow to the surface roughness in ABL flows. The simulated results obtained using the two wall functions are compared against the wind-tunnel measurements. It is shown that LES using the implemented wall function produces overall satisfactory results on the turbulent flow over the two-dimensional hills. The prediction of the flow separation and reattachment-length for the steeper hill is closer to the measurements than the other numerical studies reported in the past for the same hill geometry. The field measurement campaign performed over the Bolund hill provides the most recent field-experiment dataset for the mean flow and the turbulence properties. A number of research groups have simulated the wind flows over the Bolund hill. Due to the challenging features of the hill such as the almost vertical hill slope, it is considered as an ideal experimental test case for validating micro-scale CFD models for wind energy applications. In this work, the simulated results obtained for two wind directions are compared against the field measurements. It is shown that the present LES can reproduce the complex turbulent wind flow structures over a complicated terrain such as the Bolund hill. Especially, the present LES results show the best prediction of the turbulent kinetic energy with an average error of 24.1%, which is a 43% smaller than any other model results reported in the past for the Bolund case. Finally, the validated LES methodology is demonstrated to simulate the wind flow over the existing Muukko wind farm located in South-Eastern Finland. The simulation is carried out only for one wind direction and the results on the instantaneous and time-averaged wind speeds are briefly reported. The demonstration case is followed by discussions on the practical aspects of LES for the wind resource assessment over a realistic inland wind farm.

Geologisk kart over öerne ved Kristiania (etagen 4) : på grundlag af kart over Kristiania havnedistrikt optaget 1884 og 1885

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Geologisk kart over de Skandinaviske lande og Finland

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Kart over det sydlige Norge : efter de bedste forhaandenvaerende kilder ...

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Kart over den norske kyst fra Trondhjems leden til Tromsö ...

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Ethnographisk kart over Finmarken n:o 1 : præstegjældene : I Vardö, II Vadsö, og en deel af III Næsseby og IV Lebesby

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

Ethnographisk kart over Finmarken n:o 3 : præstegjældene : I Alten, II Koutokæino, III Hammerfest og en deel af IV Skjærvö, V Loppen og VI Maasö

Kartta kuuluu A. E. Nordenskiöldin kokoelmaan

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.

Postimerkit merisotataidon dokumentteina : Britannian ja Saksan laivastojen varustelu maailmansotien välisenä aikana

Merisodassa tapahtunut muutos – erityisesti konevoiman syrjäyttäessä purjeet ja raudan korvatessa puumateriaalin 1800-luvun loppupuolella – johti nykypäivänäkin merkittäviin merisodan teoreettisiin tarkasteluihin. Teorioihin pohjautuneet merisotataidon yleisperiaatteet saivat ensimmäisen maailmansodan aikana käytännön testauksensa. Voittajat ja häviäjät analysoivat taistelut sekä maailmalla vallinneen ripeän teknisen kehityksen, minkä seurauksena laivastojen varustelu kiihtyi uudestaan valtapolitiikan tueksi. Maailmansotien välisenä aikana pyrittiin kansainvälisin sopimuksin säätelemään suurten laivastojen, kuten Britannian, Ranskan, Italian, Japanin ja Yhdysvaltojen varustelukilpailua. Versaillesin rauhansopimus rajoitti samanaikaisesti Saksan merivoimien kokoa. Tässä työssä tutkitaan Britannian ja Saksan merivoimien varustelua ja merisotataidon kehittymistä maailmansotien välisenä aikana. Merisotataidon kehittymisen tarkastelu tapahtuu postimerkkien avulla. Postimerkki syntyi Englannissa vuonna 1840 ja sen käyttö yleistyi ympäri maailman lähes samanaikaisesti konevoimaa käyttäneiden laivojen kanssa. Postimerkkien kuva-aiheet olivat aluksi valtioiden päämiehiä, heraldiikkaa, maisemia tai abstrakteja aiheita. Vasta 1900-luvun alkupuolella kuva-aiheina saattoi olla lähes mitä vain, myös sotalaivojen kuvia. Postimerkkikokoelmastani erottuu tutkimusaiheeseen 335 merkkiä. Britannian ja Saksan kansallisarkistojen alkuperäislähteiden ja tutkimuskirjallisuuden dokumenttianalyysiin perustuvaa merisotataidon moninaista kehitystä verrataan tutkimuksessani postimerkkien kuva-aiheisiin ja niiden yksityiskohtiin 3 300 kertaa. Tällä menettelyllä pyrin selvittämään voiko postimerkkejä käyttää ja pitää merisotaidon kehityksen kattavina dokumentteina. Postimerkeissä satunnaisiksi jääneet virheet tai propaganda eivät vähennä merisotataidon kehityksen kuvaamisen dokumenttiarvoa. Postimerkkien sotalaivoihin liittyvät kuvat kattavat muutamaa laivaluokkaa lukuunottamatta molempien maiden kaikki taistelualuslajit- ja luokat. Postimerkeistä voidaan nähdä vanhat sotalaivat, niiden peruskorjaukset ja uudet luokat lentotukialuksista sukellusveneisiin. Alusten kuvat voidaan liittää Britannian kansainyhteisön muuttuneisiin strategisiin ja taktisiin tavoitteisiin niin Atlantilla kuin Kaukoidässä. Saksan merivoimien nousu Versaillesin rauhanehtojen rajoituksista ja lopulta pyrkimys Britannian kauppamerenkulun tuhoajaksi välittyy myös postimerkeistä. Yleinen sotatekninen kehitys, lentoneiden tulo merisotanäyttämölle ja aikanaan kansainvälisten tonnistorajoitusten poistuminen näkyvät postimerkeissä. Kokopostimerkin historian aikana vuoteen 2012 mennessä purjeettomien, nykyaikaisten sotalaivojen kuvia on julkaistu noin 3 350 postimerkillä, jotka on koottu Maailman suurin laivasto-osasto -postimerkkikokoelmaani noin 35 vuoden aikana