2 resultados para TRANSITION-STATE ANALOGS

em Doria (National Library of Finland DSpace Services) - National Library of Finland, Finland


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Paperikoneen telalle integroitujen mekaanisten käyttölaitteiden valmistuksen siirtoprojektin yhteydessä on raportoitu huomattavan paljon valmistuksen aikaisia poikkeamia. Poikkeamien juurisyyn hahmottamiseksi tehtiin kvantitatiivinen analyysi raportoiduista poikkeamista ja kvalitatiivinen analyysi kokoonpanon nykytilasta. Kokoonpanotyöstä suuri osa on tällä hetkellä arvoa jalostamatonta työtä. Tutkimuksessa havaittiin valmistusprosessissa kaikkia kokoonpanon poikkeamien perustyyppejä ja näitä poikkeamia olivat aiheuttaneet kaikki mahdolliset aiheuttajat. Etenkin hankittavien osien laatua tulisi käsitellä poikkeamien aiheuttamien kokonaiskustannusten kautta. Kokoonpanon tarvitsema tieto on olemassa täsmällisessä muodossa, mutta sen luoksepäästävyys on huono. Prosessin kuvauksella, hiljaisen tiedon kirjaamisella ja täsmällisen tiedon julkistamisella voidaan parantaa tuotannon laatua tuotetuntemuksen parantuessa. Käyttökohteen tunteminen parantaa vaatimusten ymmärtämistä. Tutkimuksessa havaittujen poikkeamien analysoinnin perusteella erityistä huomiota tulisi kiinnittää tarkastusvaiheiden olemassa oloon, sijoitukseen ja niiden laatuun. Suuri osa poikkeamista oli edennyt kokoonpanoon jonkin tarkastusvaiheen läpi. Tarkastusvaiheiden laatutason tulee parantua, jotta moninkertaisesta tarkastuksesta voidaan luopua.

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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.