Metallurgisk industri prøver å forene kvalitet av rå varer med relativt lav pris og den beste teknologien. Eksergi gjør det mulig å finne og kvantifisere evnen til forbedring av termiske og kjemiske prosesser. Selve eksergi applikasjonen har en betydelig rolle i å forbedre effektivitet, dette er ennå ikke vanlig i industrien.Målet med denne studien er å se på energi og eksergi fordeling i silisium prosessen ved Holla-anlegget. Produksjon av silisium metall er teknisk godt etablert. Kostnadsreduksjon er et nytt grep i modernifiseringen. Anlegget ved Holla har oppnådd reduserte kostnader ved å bruke biligere råvarer. I 2006 sluttet Holla å bruke trekull i blandingen av råvarer. Siden da har trekull bare vært brukt av og til.To analyser har blitt etablert med data fra ovn #4 ved anlegget. Den første med data samlet inn fra 2006, der trekull var inkludert i råvaren. Den andre med data fra 2001 der trekull ikke var en del av råvaren.Energi analysen avdekker store energitap som går som tapt varme. Bare 28.7 MW av 80.4 MW in den første analysen og 30.13 MW av 82 MW av energien ble levert til silisium-prosessen, kom tilbake som en kjemisk energi i produktet.Produksjon av silisium innebærer store eksergi ødeleggelse, omtrent 39,2 MW i begge analyser.

The goal of this work is the synthesis of a tocopherol/carotenoid hybridderivative (1, figure II). The novel derivative is believed to exhibitsynergistic antioxidant effects between its chromanol and polyene consituents.The synthesis of 1 was completed up to and including theimmediate precursor 12.Commercially avaliable Trolox (7) was reduced by Red-Al® to 8(step a) in 95% yield. Chromanol aldehyde 9 was formed by Swernoxidation of 8 in 65% yield (step b). Wittig reaction between 9 andphosphonium salt 10 afforded 11 in 33% yield and varying cis : transratio (step c), and subsequent elongation produced 12 (14% yield, stepd). The Wittig reactions were performed with reflux and microwaveirradiation.Various attempts at protecting the phenolic group in intermediate8 by silylation or benzylation did only lead to formation of 8B.Oxidation of 8 by the Dess-Martin oxidation formed the unexpectedquinone-like derivative 27. Efforts to protect the phenolic group in intermediate9 by benzoylation and silylation only produced 9A, foundto be unsoluble in all common laboratory solvents.

<p>Enantiomerically pure amines and alcohols are particularly important synthons for the preparation of pharmaceuticals and agrochemicals. Notwithstanding the advances that have been achieved in asymmetric synthesis, resolution of racemates is probably the most current approach for the preparation of pure enantiomers. On the other hand, resolution processes suffer from disadvantages of low yields caused by the loss of at least 50% of the undesired isomer. Among the attractive methods for avoiding the drawbacks of resolution processes is inversion of configuration of the unwanted isomer. Although there are several existing methodologies for inversion and stereoselective transformations of chiral alcohols, corresponding methods for inversion of chiral amines has received less attention. The main objective of the project “Stereoselective transformations of chiral amines” was therefore to develop effective methods for inversion and stereoselective transformations of chiral amines.</p><p>This thesis discuss the utility of three nucleophilic substitution methods in stereoselective transformations of chiral amines.</p><p>The first investigation towards this goal was carried out using cyclic aryldisulfonylimide leaving group. Substitution of a chiral amine via N,Nnaphthalene- 1,2-disulfonylimide intermediate gave azide and alcohol products with 60-73% inversion of configuration, which was 20-25% lower compared to the previously studied relative disulfonylimides. Displacement of this group using aroxide anions afforded chiral aryl ethers with 70-87% inversion of stereochemistry. Chiral analysis of the ether products required synthesis of authentic reference compounds. This was achieved via benzyne route and by nucleophilic substitution on the derivatives of chiral alcohols. The benzyne route gave chiral phenyl ether from enantiopure alcohols with complete retention of configuration while the trifluoroacetate derivatives of chiral alcohols produced chiral aryl ethers with complete inversion of stereochemistry.</p><p>The 2,4,6-triphenylpyridinium cations were the next intermediates investigated in this study. These derivatives were synthesized from 2,4,6-triphenylpyrylium tetrafluoroborate in 84-90% yields using procedures described by Katritzky. Nucleophilic substitution on pyridinium salts of aliphatic chiral amines using azide and hydroxide anions gave products with 96 to 100% inversion of configuration.</p><p>The utility of diazonium salts for inversion of chiral amines was also investigated in the present study. This method was only focused on stereoselective transformations of α-amino acids as diazotization-dediazoniation of other aliphatic amines is of little interest for organic synthesis. Diazotization of L-alanine and L-phenylalanine ethyl esters hydrochlorides using alkyl nitrites in aprotic solvents, in the presence of azide anion, yielded optically active chloro substituents as the only products, instead of the intended azide compounds. Attempts to avoid counterion substitution by using ammonium tosylate to replace the ammonium chlorides was not useful and a tosyl product was isolated instead. Proposals to rectify this problem have been suggested. These include the use of much more inert counterions such as tetrafluoroborate or replacing the hydrochlorides with hydroazides. An alternative which could deliver the nucleophile in an intramolecular fashion has also been postulated. Investigations of these hypotheses are currently conducted.</p><p>Parallel to diazotization reactions was an investigation on inversion of α-amino acids via N,N-disulfonylimides and 2,4,6-triphenylpyridinium cation leaving groups. Studies with N,N-disulfonylimide derivatives showed that this leaving group is not useful for inversion of α-amino acids. Nucleophilic substitution on the 2,4,6-triphenylpyridinium salts of amino acids afforded partial racemized substitution products. The drawback in the utility of the pyridinium salts has been identified and efforts are underway to remove this impediment.</p>

Enantiomerically pure amines and alcohols are particularly important synthons for the preparation of pharmaceuticals and agrochemicals. Notwithstanding the advances that have been achieved in asymmetric synthesis, resolution of racemates is probably the most current approach for the preparation of pure enantiomers. On the other hand, resolution processes suffer from disadvantages of low yields caused by the loss of at least 50% of the undesired isomer. Among the attractive methods for avoiding the drawbacks of resolution processes is inversion of configuration of the unwanted isomer. Although there are several existing methodologies for inversion and stereoselective transformations of chiral alcohols, corresponding methods for inversion of chiral amines has received less attention. The main objective of the project “Stereoselective transformations of chiral amines” was therefore to develop effective methods for inversion and stereoselective transformations of chiral amines. This thesis discuss the utility of three nucleophilic substitution methods in stereoselective transformations of chiral amines. The first investigation towards this goal was carried out using cyclic aryldisulfonylimide leaving group. Substitution of a chiral amine via N,Nnaphthalene- 1,2-disulfonylimide intermediate gave azide and alcohol products with 60-73% inversion of configuration, which was 20-25% lower compared to the previously studied relative disulfonylimides. Displacement of this group using aroxide anions afforded chiral aryl ethers with 70-87% inversion of stereochemistry. Chiral analysis of the ether products required synthesis of authentic reference compounds. This was achieved via benzyne route and by nucleophilic substitution on the derivatives of chiral alcohols. The benzyne route gave chiral phenyl ether from enantiopure alcohols with complete retention of configuration while the trifluoroacetate derivatives of chiral alcohols produced chiral aryl ethers with complete inversion of stereochemistry. The 2,4,6-triphenylpyridinium cations were the next intermediates investigated in this study. These derivatives were synthesized from 2,4,6-triphenylpyrylium tetrafluoroborate in 84-90% yields using procedures described by Katritzky. Nucleophilic substitution on pyridinium salts of aliphatic chiral amines using azide and hydroxide anions gave products with 96 to 100% inversion of configuration. The utility of diazonium salts for inversion of chiral amines was also investigated in the present study. This method was only focused on stereoselective transformations of α-amino acids as diazotization-dediazoniation of other aliphatic amines is of little interest for organic synthesis. Diazotization of L-alanine and L-phenylalanine ethyl esters hydrochlorides using alkyl nitrites in aprotic solvents, in the presence of azide anion, yielded optically active chloro substituents as the only products, instead of the intended azide compounds. Attempts to avoid counterion substitution by using ammonium tosylate to replace the ammonium chlorides was not useful and a tosyl product was isolated instead. Proposals to rectify this problem have been suggested. These include the use of much more inert counterions such as tetrafluoroborate or replacing the hydrochlorides with hydroazides. An alternative which could deliver the nucleophile in an intramolecular fashion has also been postulated. Investigations of these hypotheses are currently conducted. Parallel to diazotization reactions was an investigation on inversion of α-amino acids via N,N-disulfonylimides and 2,4,6-triphenylpyridinium cation leaving groups. Studies with N,N-disulfonylimide derivatives showed that this leaving group is not useful for inversion of α-amino acids. Nucleophilic substitution on the 2,4,6-triphenylpyridinium salts of amino acids afforded partial racemized substitution products. The drawback in the utility of the pyridinium salts has been identified and efforts are underway to remove this impediment.

Hovedmålet i masteroppgaven har vært å utforske nye gullkatalyserte reaksjoner og anvendelser av propargylestere og allenestere. Allen 14, ble syntetisert fra propargylbromid over to trinn, ved en kjent prosedyre. Kationiske gullkomplekser har en sterk alkynofil karakter som aktiverer alle typer &#960;-systemer for nukleofilt angrep. Dette gjør allen 14 godt egnet som substrat i gullkatalyserte transformasjoner. E-Dien 22a-b, samt Z-dien 23a-b, ble syntetisert i en stereoselektiv gull(I)katalysert reaksjon. Dette er første gang diener har blitt fremstilt fra 2-substituerte allenestere, og det ble observert en høyere Z-selektivitet enn hva som tidligere har blitt observert for usubstituerte allenestere. Dien 22a og 23a ble isolert i et utbytte på henholdsvis 35% og 33% med et E/Z-forhold på 47:53. For dien 22b og 23b var E/Z-forholdet 52:48, og de ble isolert utbytter på 38% og 28%. Elektrofil addisjon til allen 14, etterfulgt av et 1,2-arylskift, ga aldehyd 25 i et utbytte på 45%. Tre nye forbindelser er blitt fremstilt ved en helt ny metode for gull(I)katalysert jodhydroksylering av allenestere. Vinyljodid 24 og 26 ble dannet i utbytter på henholdsvis 59% og 39%, mens omleiret produkt 27, ble isolert i et utbytte på 20%. Syklopropylforbindelse 28 ble syntetisert i en ny gull(I)katalysert ”tandem”-syklopropaneringsreaksjon, fra propargylester 4, i et utbytte på 34%.Fire nye syklopropylforbindelser 18a-b og 19a-b har blitt syntetisert. Disse er dannet i en sykliseringsreaksjon mellom vinylester 17 og propargylester 1b eller 4. Syklopropylforbindelse 18 og 19 er isolert i utbytter på henholdsvis 52% og 76%. Et kiralt NHC-basert gullkompleks 41 har blitt syntetisert, og testet som gull-ligand i syklopropanerings-reaksjon. Det ble funnet et enantiomert overskudd på 5% for cis-forbindelse 43a, og et enantiomert overskudd på 6% for trans-forbindelse 43b. Dette er første gang en kiral NHC-basert gullkatalysator er blitt testet i en gullkatalysert asymmetrisk syklopropaneringsreaksjon.

Et kiralt triazoliumbasert N-heterosykliskkarben-salt (NHC) 1 har blitt fremstilt fra L-fenylalanin 2 og fenylhydrazinhydroklorid 12 i en synteserute som går over fem trinn, og med et totalutbytte på 10%. NHC-salt 1 er blitt testet som organokatalysator i en sykliseringsreaksjon mellom aldehyd 4 og keton 5. Produktet, butyrolakton 6, ble dannet i et trans/cis-forhold på 59:41, og med et enantiomert overskudd på henholdsvis 10% og 19% for trans- og cis-forbindelse 6a og 6b.NHC-salt 1 ble testet som ligand i en gullkatalysert syklopropaneringsreaksjon. Gullkatalysator 15a og 15b ble syntetisert fra NHC-salt 1 og 16 ved hjelp av Ag2O og AuCl(Me2S) i et utbytte på henholdsvis 82% og 85%. Syklopropaneringsreaksjon mellom alkyn 18 og alken 19 ga syklopropylforbindelse 20 i et trans/cis-forhold på 41:59 for gullkatalysator 15a og 38:62 for gullkatalysator 15b. Gullkatalysator 15a ga et enantiomert overskudd på 8% og 6% for henholdsvis trans- og cis-forbindelse 20a og 20b. Gullkatalysator 15b ga et enantiomert overskudd på 10% og 9% for de samme forbindelsene. Dette er første gang en kiral triazolbasert NHC-gullkatalysator har blitt brukt i asymmetrisk syntese.

This project looks at the capillary systems with salt water and oil that can be found in porous stones in oil reservoir. The interactions between the different phases and how salt concentration differences can move the oil. The first problem was to find how the water migrates from one side of an oil droplet to the other due to the concentration difference. This was discussed, but not experimentally verified. The reason for this is the high inaccuracy of the experiments and the lack of knowledge before starting. However, this project gives a lot of important knowledge about the problem, and good suggestions for improvements. It was experimentally confirmed that oil is moving due to the difference in salt concentration. From this, the diffusion coefficient was found and reported to be D = (1.08 &#177; 0.10) &#183; 10&amp;#8722;7 m2/s for glass capillary tubes of radius 0,70 mm and at 60oC, calculated from the phenomenological coefficient L that was found. It was also confirmed that the capillary force does not contribute significantly for this size of the tubes, and therefore L should be independent of the radius. The maybe most interesting result of the experiments and calculations is that the capillary force will contribute significantly to the total force and then also the movement of the oil droplet. This does not happen before the radius of the tubes where under 0,20 mm. The experiments and the estimates agreed well with the radius where the change happens.

Hindering the degradation of amines in the CO2-capturing process is important both for economical purposes when it comes to loss of solvent and impacts on the process, and to prevent emissions of volatile degradation compounds such as ammonia, nitrosamines and formaldehyde. To prevent the absorbent from degrading, either a non-degrading absorbent can be developed or a degradation inhibitor can be added to minimize the degradation. The degradation inhibitors tested in this thesis are meant to inhibit the oxidative degradation that mainly occurs in the absorber. The carbamate polymerization degradation due to CO2 and temperature has to be addressed on its own. The inhibitor screening apparatus was new, and a part of the assignment was testing this setup. The first experiment conducted on the inhibitor screening apparatus used a gas blend of 6% O2/2 % CO2 (N2 balance). This did not give enough degradation, which caused the need for rebuilding the rig. In the other experiments on the screening apparatus, a gas composition of 98 % O2/2 % CO2 was used to get sufficient amount of degradation for inhibitor screening. Inhibitor screening experiments were done using 150 mL of a 30 weight% (wt%) 2-aminoethanol (MEA) solution loaded with 0,4 mol CO2/mol MEA, at 55 &#176;C with a gas flow of 10 mL/min. To test the stability of the inhibitors at higher temperature, thermal experiments with inhibitors were conducted. 7 mL solution was filled in stainless steel cylinders and heated at 135 &#176;C, for a period of five weeks. The solution was 30 wt% MEA loaded with 0,5 mol CO2/mol MEA. Hydrazine was screened for inhibitory effect using a circulative closed loop apparatus because of the hazards related to this compound. The experiment was run with air, using a 30 wt% MEA solution loaded with 0,4 mol CO2/mol MEA, at 55 &#176;C. Since experiments with both 6 % and 98 % oxygen were conducted, it was natural to compare the impact of oxygen concentration on the degradation products. Results indicated that 2-oxazolidinone (OZD) was preferred at the conditions with high oxygen, while N-(2-hydroxyethyl) glycine (HeGly) concentrations increased with decreasing oxygen content. The effect of metals on product composition was also investigated. The degradation compound N-(2-hydroxyethyl) imidazole (HEI) seems to be dependent on the metal concentrations, increasing in the presence of metals. For the inhibitors screened, the inhibition ranged from 23,59-67,81 %. Two compounds gave an increase in degradation. 1-hydroxyethane 1,1-diphosphonic acid (HEDP) was the only chelating agent stable at thermal conditions. The inhibitors did not appear to have a substantial effect on the carbamate polymerization. Quantification of degradation compounds in the samples was done using liquid chromatography-mass spectrometry (LC-MS) and anion chromatography-electrochemical detector (IC-EC). Amine loss and CO2-loading were determined using titration methods. Metal concentrations were determined using inductively coupled plasma-mass spectrometry (ICP-MS). Some analyses were done gravimetrically while others were done volumetrically. For comparison purposes, simple density measurements were done, and the data converted according to the amine loss in the sample.The initial intention was to use gas chromatography - mass spectrometry (GC-MS) to analyze the samples from the thermal experiments. The system was however not operable during the time available. ICP-MS analysis was not done in time for the last experiment. Ammonia analyses were not conducted in time for this thesis.

The goal of this work was the synthesis of a carotenoid cationic lipid for the research of carriers of nucleic acids into defective cells via transfection therapy. In the course of this project a precursor for the carotenoid cationic lipid was successfully obtained, but because of the limited time the synthesis of the carotenoid cationic lipid itself was not performed.

Through this study it has been observed that in contrast to propargyl esters which give cyclopropyl products, the high reactivity of propargyl acetals allows a new tandem cyclization to take place, resulting in bicyclic products. It has also been found that steric effects may cause propargyl acetals to react by unexpected pathways. NMR studies confirmed a particularly high reactivity of propargyl acetal compared to propargyl ester. These results show how molecular diversity can easily be achieved by varying the substrates in gold(I) catalysis.