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1
Gobina, E. N. "N-butane oxidation on vanadium-phosphorus-oxide catalysts." Thesis, University of Newcastle Upon Tyne, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.304565.
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Brandstädter, Willi Michael. "Partial oxidation of raffinate II and other mixtures of n-butane and n-butenes to maleic anhydride in a fixed-bed reactor." Karlsruhe Univ.-Verl. Karlsruhe, 2007. http://d-nb.info/987418661/04.
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Davies, Michael John. "The heterogeneously catalysed selective oxidation of n-butane to maleic anhydride." Thesis, Imperial College London, 1990. http://hdl.handle.net/10044/1/46275.
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Andaka, Ganjar. "The catalytic oxidation of n-butane to maleic anhydride using a membrane reactor." Thesis, University of Salford, 2004. http://usir.salford.ac.uk/26550/.
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Catalytic oxidation of n-butane is important in an attempt towards developing economical and environmentally friendly processes for production of maleic anhydride. Methods of preparation of both the vanadium-phosphorus-oxides (VPO) catalyst and an inorganic composite membrane as well as the performance of the membrane obtained have been investigated in this work. The procedure used in the preparation of vanadium-phosphorus-oxides (VPO) catalyst was similar to that described by Katsumoto and Marquis (1979), while a dip coating method was used for preparation of a silica coated y-A^Os membrane from the outside, and the membrane prepared then was tested for permeance using nitrogen and air. The kinetics of the selective oxidation of n-butane to maleic anhydride has been studied over vanadium-phosphorus-oxides (VPO) catalyst in a differential glass reactor in the temperature range of 380 - 480°C and at atmospheric pressure. Apart from maleic anhydride (MA), the other detectable products were carbon monoxide (CO), carbon dioxide (CO2), and air (HhO). Kinetic measurements demonstrated the production of maleic anhydride, carbon monoxide, and carbon dioxide as initial products of the reaction at low n-butane conversion. Under conditions of a large excess of oxygen, the reaction model was represented according to a scheme of three parallel formation reactions. The activation energies for maleic anhydride (MA), carbon monoxide (CO), and carbon dioxide (CO2) production are 61.1 kJ/gmol, 56.1 kJ/gmol, and 70.9 kJ/gmol, respectively. These values of the activation energies are in the same range as those obtained from previous differential reactor studies. The oxidation of n-butane to maleic anhydride also has been compared by using fixedbed and membrane reactors with the same VPO catalyst. The effects of operating conditions on the conversion of n-butane, the selectivity to maleic anhydride, and the yield of maleic anhydride have been studied in detail. A simulation study on the use of fixed-bed and membrane reactors for oxidation of n-butane to maleic anhydride has also been undertaken. The results of a mathematical simulation study were compared with the experimental results. The membrane reactor offers several advantages over the fixed-bed reactor for selective oxidation of n-butane to maleic anhydride. The membrane reactor provides a wider operating range particularly with respect to inlet gas composition. Furthermore, they are inherently safer since n-butane and oxygen feeds can be separated by the membrane. The higher butane concentrations and controlled addition of oxygen along the reactor length by means of a membrane lead to higher product rates. A comparative study of butane oxidation to maleic anhydride in conventional fixed-bed and a membrane reactor show that using a membrane reactor gives a better selectivity and yield of maleic anhydride than the conventional fixed-bed reactor. From the simulation study, the mathematical models for both the fixed-bed and membrane reactors are in good agreement with the experimental results, except for the mathematical model for the fixed-bed reactor when considering the variation of the oxygen/n-butane ratio. For the membrane reactor, both feed n-butane concentration and oxygen/butane ratio are shown to be not sensitive parameters for the mathematical model, while temperature is a key parameter.
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Al-Otaibi, Raja Lafi. "Preparation and characterisation at vanadium phosphorus oxide catalysts for butane oxidation to maleic anhydride." Thesis, Cardiff University, 2010. http://orca.cf.ac.uk/54234/.
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Vanadium phosphate catalysts have successfully been prepared in aqueous media using hydrogen. The catalysts precursors obtained were poorly crystalline VOHPO4.05H2O and a minor amount of an impurity detected by a reflection in the XRD pattern. Activating these materials for n-butane oxidation show low selectivity of MA (5%), which could be attributed to the presence of V(V) phases after activation.
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Lynch, Michelle Katherine. "The catalytic vapour phase oxidation of butane to acetic acid over vanadium oxide catalysts." Thesis, University of Reading, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263068.
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Ye, Yinmei. "Experimental study on n-Butane partial oxidation to maleic anhydride in a solid electrolyte membrane reactor Experimentielle Untersuchung der partiellen Oxidation von n-Butan zu Maleinsäureanhydrid in einem Festelektrolytmembranreaktor /." [S.l.] : [s.n.], 2006. http://deposit.ddb.de/cgi-bin/dokserv?idn=979547164.
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Brandstädter, Willi Michael. "Partial oxidation of raffinate II and other mixtures of n-butane and n-butenes to maleic anhydride in a fixed-bed reactor." Karlsruhe : Universitätsverlag, 2008. http://www.uvka.de/univerlag/volltexte/2008/295/.
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Chakir, Abdelkhaleq. "Etude cinetique et modelisation du mecanisme d'oxydation a haute temperature de n-butane et de 1-butene." Paris 6, 1988. http://www.theses.fr/1988PA066132.
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L'etude experimentale de l'oxydation du butane et du butene-1 a ete effectuee en reacteur auto-agite par jets gazeux dans un large domaine de conditions experimentales (900-1200 k, 1 a 10 atm, rapports d'equivalents oxygene-hydrocarbure 0,1-4)
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Salazar, Juan Manuel. "Sol-gel synthesis of vanadium phosphorous oxides for the partial oxidation of n-butane to maleic anhydride." Diss., Manhattan, Kan. : Kansas State University, 2007. http://hdl.handle.net/2097/428.
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Sithamparappillai, Umacaran. "Influence of the reaction conditions on the synthesis of vanadium phosphate catalyst for butane oxidation to maleic anhydride." Thesis, Cardiff University, 2008. http://orca.cf.ac.uk/55746/.
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Vanadium phosphate catalysts prepared by the reduction of VOPO4.2H2O with 1-butanol are described and discussed. In particular, the effect of the addition of an alkane during the reflux stage of the preparation has been investigated. The materials were characterised using a combination of powder XRD, BET surface area measurement, laser Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The addition of C(, - Ci 6 w-alkanes was studied and has been observed to significantly affect both the morphology and the structure of the vanadium phosphates. In the absence of an alkane VOPO42H2O is reduced to VOHPO4O 5H2O with rosette morphology. Addition of low amounts of alkanes leads to a change in the crystallite morphology and platelet crystallites are preferentially formed. Decreasing the alcohol concentration further leads to the formation of VO(H2PC4)2, with its characteristic block-shaped crystallites. The amount of alkane required to induce these changes decreased with increasing carbon number of the n-alkane. Furthermore, the different concentration of the alcohol results in a different reduction rate of V5+ to V4+ which changes the V: P ratio of the prepared materials. Therefore, different materials were obtained with respect to V: P ratio. Evaluation of the materials as catalysts for the oxidation of butane to maleic anhydride shows that the materials exhibit their characteristic activities and selectivities for this reaction. A new synthesis route has been developed to prepare (VO)2P2C7 directly from VOPO42H2O using a reducing environment. Hydrogen (5% H2/Argon 50 ml // min) was used for this transformation for 72 hours at temperature 550 C. The specific activity of these materials is higher than the conventional catalysts due to the low surface area.
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Bartley, Jonathan Keith. "The preparation and characterisation of vanadium phosphate catalysts for the selective oxidation of n-butane to maleic anhydride." Thesis, University of Liverpool, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.366683.
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Brandstädter, Willi Michael [Verfasser]. "Partial oxidation of raffinate II and other mixtures of n-butane and n-butenes to maleic anhydride in a fixed bed reactor / von Willi Michael Brandstädter." Karlsruhe : Univ.-Verl. Karlsruhe, 2008. http://d-nb.info/987625942/34.
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Le, Tan Ngoc Linh. "Mesure d’intermédiaires réactionnels (HO2, H2O2, CH2O) par CRDS lors de la combustion du n-butane et de l’éther di-méthylique et simulations cinétiques." Thesis, Orléans, 2015. http://www.theses.fr/2015ORLE2027.
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La mesure de la formation de HO2 et H2O2 lors de l’oxydation de carburant est très difficile. Par contre, elle est extrêmement importante pour déterminer l’importance relative des voies de terminaison de chaînes de R + O2 et de ramification des chaînes menant à la production des radicaux OH. Par ailleurs, ces informations sont essentielles pour améliorer les modèles cinétiques. Afin de répondre à cette demande, un nouveau dispositif expérimental a été développé dans notre laboratoire : un réacteur auto-agité par jets gazeux couplé à un détecteur cw-CRDS qui permet d’analyser en ligne des produits de combustion. Grâce à ce nouveau système, pour la première fois, HO2 a été mesuré directement lors de l’oxydation du n-butane et de l’éther di-méthylique dans un réacteur auto-agité par jets gazeux. L’échantillonnage est toujours à basse pression et les produits sont détectés dans le proche infrarouge. Toutes nos expériences ont été réalisées à pression atmosphérique dans le domaine de température 500-900 K. Les produits de combustion mesurés sont CH2O, H2O2, HO2, C2H4 et H2O. Nos résultats expérimentaux ont été utilisés pour tester des modèles cinétiques issus de la littérature que nous avons analysés en menant des analyses de sensibilité et de voies réactionnellesMeasuring the formation of HO2 and H2O2 from the oxidation of fuels is challenging but extremely important for determining their tendency to follow chain-termination pathways from R+O2 compared to chain-branching leading to the production of OH radicals. Furthermore, such data are vital for improving existing detailed chemical kinetics models. In order to meet these requirements, a new experimental setup has been developed in our laboratory: a jet-stirred reactor coupled with the cw-CRDS, which allows analyzing online combustion products. Thanks to this new system, for the first time, HO2 was measured directly during the oxidation of n-butane and dimethylether in a jet-stirred reactor. The sampling is always in vacuum and the species were detected at near infrared. All of our experiments were carried out at atmospheric pressure and in the range of temperature between 500 K to 900 K. The combustion products measured were CH2O, H2O2, HO2, C2H4, and H2O. Our experimental results were used to test published kinetic models that were analyzed by performing sensitivity and reaction paths analyzes
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Gabano, Jean-Denis. "Etude dans une chambre fermée du régime de combustion vibratoire s'apparentant au cliquetis des moteurs alternatifs à allumage commandé." Poitiers, 1988. http://www.theses.fr/1988POIT2293.
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Etude du cliquetis dans les moteurs a explosion. Etude de la combustion, de la flamme et de l'antiinflammation. On utilise la cinematographie ultrarapide et l'enregistrement des emissions en lumiere bleue. Problemes de traitement de signal. Mise en evidence de prereactions d'oxydation a basse temperature
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Kah, Stefan. "Entwicklung und Einsatz von Mikrostrukturreaktoren mit katalytisch wirksamen Strömungskanälen für die partielle Gasphasen-Oxidation von 1-Buten." Doctoral thesis, Universitätsbibliothek Chemnitz, 2005. http://nbn-resolving.de/urn:nbn:de:swb:ch1-200400981.
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In der vorliegenden Arbeit wurden erstmalig Mikrostrukturreaktoren bei der partiellen Oxidation von 1-Buten zu Maleinsäureanhydrid (MSA) eingesetzt. Diese stark exotherme, heterogen katalysierte Umsetzung fand hierbei in Stapeln mikrostrukturierter Aluminiumfolien statt, welche durch parallele Strömungskanäle mit katalytisch wirksamen Oberflächenschichten charakterisiert sind. Als Aktivkomponenten kamen Vanadium-, Phosphor- und Titanoxide zur Anwendung. Ein Vergleich von drei kompakten Mikrostrukturreaktoren mit Kanaldurchmessern der Mikrokanäle von 0,08, 0,2 bzw. 0,4 mm mit einem Schüttgutreaktor wurde durchgeführt. Vorausgehend war die Entwicklung von 3 verschiedenen Methoden zur Immobilisierung von V2O5 und P2O5 auf dem Katalysatorträger bei jeweils unterschiedlichen Katalysatorvorläufern. Die Herstellungsparameter der geeignetsten Immobilisierungsmethode wurden, entsprechend einem Screening in Schüttgutreaktoren, systematisch variiert. Die katalytische Aktivierung der Folien erfolgte nach der gleichen Präparationsvorschrift die zur Herstellung des besten Katalysator-Schüttguts führte. Bei der partiellen Oxidation von 1-Buten außerhalb des Explosionsbereiches bestanden nur geringfügige Unterschiede zwischen den MSA-Selektivitäten im Schüttgut bzw. in der Mikrostruktur (33%). In letzterer wurden hingegen um den Faktor 3 bis 5 höhere Raum-Zeit-Ausbeuten als im Schüttgut erzielt. Des weiteren konnte die partielle Oxidation von 1-Buten innerhalb des Explosionsbereiches ausschließlich in den Mikrostrukturreaktoren explosionssicher - und ohne Anzeichen auf instabile Betriebspunkte gehandhabt werden. Begleitend dazu fand die Entwicklung und der Einsatz dreier modularer Mikrostrukturreaktoren bei der partiellen Oxidation von 1-Buten statt. Praktische Ergebnisse wurden anhand eines entwickelten Reaktormodells bestätigt.
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Kah, Stefan. "Entwicklung und Einsatz von Mikrostrukturreaktoren mit katalytisch wirksamen Strömungskanälen für die partielle Gasphasen-Oxidation von 1-Buten." [S.l. : s.n.], 2004. http://archiv.tu-chemnitz.de/pub/2004/0098.
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Ingham, Trevor. "The direct oxidation of trans-2-butene and iso-butene between 400 and 500 degrees centigrade." Thesis, University of Hull, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.296221.
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Fenard, Yann. "Etude expérimentale et modélisation de l’oxydation de composés organiques à des fins de sécurité industrielle : cinétique d’oxydation des butènes (1-, cis-2-, trans-2- et iso-)." Thesis, Orléans, 2014. http://www.theses.fr/2014ORLE2059/document.
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Dans le cadre du projet DISPATMO (étude de la prévision des risques de pollution liés à la dispersion atmosphérique de produits chimiques), des études de risques liés aux incendies et explosions dus aux produits chimiques stockés sur deux sites tests ont été menées. Le but est d’identifier les produits de combustion de certains composés cibles définis au début du projet, ainsi que d’estimer leur concentration. Les composés tests sont l’éthanol, le 2-butanone, le toluène et le solvant TIFLEX. Ces composés sont susceptibles, surtout à richesse élevées, de former des quantités non-négligeables d’isomères du butène, composés chimiques connus pour être d’importants intermédiaires de la combustion d’hydrocarbures. Après une étude bibliographique sur les isomères du butène, de l’éthanol, de la 2-butanone et du toluène, un mécanisme cinétique détaillé pour simuler l’oxydation de ces composés a été proposé. Une étude expérimentale de l’oxydation de 4 butènes (1-butène, trans-2-butène, cis-2-butène et iso-butène) a été réalisée en réacteur auto-agité (T = 900-1440 K, p = 1 atm, = 0,25, 0,5, 1 et 2, = 70 ms) et en chambre de combustion sphérique (Ti = 300 K, pi = 1, 2, 3 et 5 atm, = 0,8-1,4). Les résultats obtenus ont été confrontés à la simulation. Des données expérimentales issues de la littérature ont été utilisées afin de valider le modèle pour l’oxydation de l’éthanol, de la 2-butanone, du toluène et des isomères du butène. Enfin, une étude expérimentale de l’oxydation du solvant TIFLEX a été menée en réacteur auto-agité (T = 740-1310 K, p = 1 atm, = 0,5, 1 et 2) pour en connaître la composition ainsi que pour identifier et quantifier les produits d’oxydation. Le mécanisme cinétique proposé comporte un coeur C0-C4 robuste, en faisant un outil prédictif fiable, pouvant servir de base à des mécanismes plus étendus capables de représenter la combustion de nombreuses autres espèces (alcanes, alcènes, alcools, aldéhydes ou cétones), par ajout de sous-mécanismesIn the context of the DISPATMO project (study of the forecast of the risks of pollution related to the atmospheric dispersal of chemicals), risk studies linked to the fires and the explosions due to chemical storage were conducted. The purpose is to identify the combustion products of certain target compounds defined at the beginning of the project, as well as to estimate their concentration. The target compounds include ethanol, 2-butanone, toluene and the solvent TIFLEX. These compounds lead, especially in fuel-rich conditions, to the formation of high quantities of butene isomers, compounds known as important intermediates of hydrocarbon combustion. After a bibliographical study on butene isomers, ethanol, 2- butanone and toluene, a detailed kinetic mechanism for the simulation of the oxidation of these compounds was proposed. An experimental study of the oxidation of the butene isomers was performed in a jet-stirred reactor (T = 900-1440 K, p = 1 atm, = 0.25, 0.5, 1 and 2, = 70 ms) and in a spherical combustion chamber (Ti = 300 K, pi = 1, 2, 3 and 5 atm, = 0.8-1.4). Experimental results were compared with their simulations. Experimental data from the literature were used to validate the model for the oxidation of ethanol, 2-butanone, toluene and butene isomers. Finally, an experimental study of the oxidation of the solvent TIFLEX was performed in the jet-stirred reactor (T = 740-1310 K, p = 1 atm, = 0.5, 1 and 2) in order to know the composition as well as to identify and quantify of the oxidation products. The proposed kinetic mechanism contains a strong C0-C4 base, resulting in a reliable predictive tool, which can be used as a base in larger mechanisms simulating the combustion other species (alkanes, alkenes, alcohols, aldehydes or ketones), by addition of sub-mechanisms
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Stothard, Nigel David. "The oxidation of trans-2-butene and propene between 400 and 520 degree C." Thesis, University of Hull, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.333710.
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Manton, Mark Richard Stening. "Oxidation of butene over platinum catalysts in a zirconia-yttria electrochemical reactor." Thesis, Massachusetts Institute of Technology, 1986. http://hdl.handle.net/1721.1/15050.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1986.MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE.
Bibliography: leaves 274-283.
by Mark Richard Stening Manton.
Ph.D.
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Freitas, Mayara Lutchemeyer de. "EFEITOS DA OXIMA BUTANO-2,3-DIONATIOSSEMICARBAZONA FRENTE AO DANO TESTICULAR CAUSADO POR CÁDMIO EM CAMUNDONGOS." Universidade Federal de Santa Maria, 2014. http://repositorio.ufsm.br/handle/1/5991.
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Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorWe investigated the action of butane-2,3-dione thiosemicarbazone oxime against the testicular damage caused by cadmium chloride (CdCl2) in mice swiss adult male. The animals received a single injection of CdCl2 at the dose of 5 mg/kg, intraperitoneally, and after thirty minutes, the oxime was administered subcutaneously at the dose of 10 mg/kg. Twenty four hours after administration of the oxime, the animals were euthanized the blood were collected and after killed the testes were removed for analysis. The parameters determined were δ-aminolevulinate dehydratase (δ-ALA-D), myeloperoxidase (MPO), glutathione-S-transferase (GST) and glutathione peroxidase (GPx) activities, in testicular tissue. The levels of thiobarbituric acid-reactive substances (TBARS), nonprotein thiols (NPSH), ascorbic acid and the quantity of cadmium in testes were also evaluated. In addition, levels of testosterone in serum and cytokines (proinflammatory, IL-1, IL-6, TNF-α, IFN-γ and anti-inflammatory IL-10) were determined. Histological analysis of testicular tissue was also performed. Our results demonstrated that the oxime was effective in restoring partially the inhibition in δ-ALA-D activity induced by CdCl2. The activation of MPO and increase in IL-1, IL-6, TNF-α and IFN-γ levels induced by CdCl2 were also reduced by oxime. IL-10, which was reduced by cadmium, was partially restored by oxime administration. In addition, the oxime was effective in restoring the increase in TBARS levels and partially the reduction on NPSH levels induced by CdCl2. However, the oxime did not have action on the decreased levels of ascorbic acid induced by CdCl2 or on the decrease in enzymatic activity of GST and the increased enzymatic activity of GPx caused by CdCl2. Our results demonstrated that oxime was effective in restoring the histological alterations induced by CdCl2, preventing the loss of elongated spermatids. In addition, oxime was able to increase the testosterone levels reduced by cadmium exposure. In conclusion, the oxime tested was effective in reducing the testicular damage induced by CdCl2 in mice. The beneficial effects of this oxime are related to its antioxidant and anti-inflammatory action.
Investigamos a ação da oxima butano-2,3-dionatiossemicarbazona contra o dano testicular causado por cloreto de cádmio (CdCl2) em camundongos swiss adultos machos. Os animais receberam uma única injeção de CdCl2 na dose de 5mg/kg, intraperitonialmente e, após trinta minutos, foi administrada a oxima subcutâneamente na dose de 10 mg/kg. Vinte quarto horas após a administração da oxima, os animais foram anestesiados o sangue foi coletado, após a eutanásia tiveram os testículos removidos para as análises. Os parâmetros determinados foram as atividades das enzimas δ-aminolevulinato desidratase (δ-ALA-D), mieloperoxidase (MPO), glutationa-S-transferase (GST) e glutationa peroxidase (GPx), no tecido testicular. Os níveis de substâncias reativas ao ácido tiobarbitúrico (TBARS), tióis não protéicos (NPSH), ácido ascórbico e quantidade presente de cádmio nos testículos também foram avaliados. Além dos níveis de testosterona no soro, onde também se quantificou as citocinas (pró-inflamatórias IL-1, IL-6, TNF-α, IFN-γ e anti-inflamatória, IL-10). Também foi realizada a análise histológica de tecido testicular. Nossos resultados demonstraram que a oxima foi efetiva em restaurar parcialmente a inibição da atividade da enzima δ-ALA-D induzida por CdCl2. A ativação da MPO e o aumento dos níveis de IL-1, IL-6, TNF-α e IFN-γ induzidos por CdCl2 também foram reduzidos pela oxima. A IL-10, que foi reduzida pelo cádmio, teve seus níveis restaurados parcialmente pela oxima. Além disso, a oxima foi efetiva em restaurar o aumento nos níveis de TBARS e parcialmente a redução nos níveis de NPSH induzidos pelo CdCl2. Porém, não teve ação sobre a queda dos níveis de ácido ascórbico provocado pelo CdCl2, nem sobre a diminuição da atividade enzimática da GST e sobre o aumento da atividade enzimática da GPx causados pelo CdCl2. Nossos resultados demonstraram que a oxima foi efetiva em conter as alterações histológicas causadas pelo CdCl2, prevenindo a perda de espermátides alongadas. A oxima também foi capaz de aumentar os níveis de testosterona reduzidos pela exposição ao cádmio. Em conclusão, a oxima testada foi efetiva em reduzir os danos testiculares induzidos pelo CdCl2. Os efeitos benéficos desta oxima estão relacionados às suas propriedades antioxidantes e sua ação anti-inflamatória.
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McNamara, John Martin. "An evaluation of alumina suppoted platinum catalysts for the oxidative dehydrogenation of n butane." Thesis, University of Glasgow, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.289903.
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Sluyter, Gerrit [Verfasser], and Andreas [Akademischer Betreuer] Liese. "Entwicklung und Charakterisierung einer fermentativen Oxidation von Butan im Blasensäulenreaktor / Gerrit Sluyter ; Betreuer: Andreas Liese." Hamburg : Universitätsbibliothek der Technischen Universität Hamburg-Harburg, 2019. http://d-nb.info/1193575311/34.
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Brumby, Charlotte Amelia. "Development of OH detection and reactivity techniques with applications to butanol oxidation." Thesis, University of Leeds, 2017. http://etheses.whiterose.ac.uk/17801/.
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The work presented in this thesis utilises the HIRAC chamber for the development and characterisation of instrumentation for measurements of OH and HO₂ radicals, and OH reactivity. This instrumentation is implemented, alongside other standard measurements, following oxidation of processes of butanol, a potential biofuel, focussing on OH reactivity and ozone formation. Results from further development of calibration methods for determining the sensitivity of a FAGE instrument are presented.
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May, Alexander [Verfasser]. "Das Reaktor-Regenerator-System als neues Konzept für die getrennte Reaktionsführung bei der selektiven Oxidation von n-Butan zu Maleinsäureanhydrid / Alexander May." Aachen : Shaker, 2003. http://d-nb.info/1179024788/34.
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Dittmer, Arne [Verfasser], Martin [Akademischer Betreuer] Muhler, and Wolfgang [Akademischer Betreuer] Grünert. "Synthesis and characterization of bismuth tungstate-supported molybdena catalysts for the selective oxidation of propene and 1-butene / Arne Dittmer. Gutachter: Martin Muhler ; Wolfgang Grünert." Bochum : Ruhr-Universität Bochum, 2016. http://d-nb.info/1099703824/34.
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Liu, Wei. "Preparation, characterization, and catalytic properties of alkaline earth oxide MO (M=Ca, Mg, Sr, Ba)--modified VOx/SBA-15 catalysts for the oxidative dehydrogenation of n-butane." HKBU Institutional Repository, 2007. http://repository.hkbu.edu.hk/etd_ra/885.
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Sedjame, Henri-Joël. "Élaboration de matériaux catalytiques pour l'élimination de polluants organiques en phase gaz." Thesis, Poitiers, 2013. http://www.theses.fr/2013POIT2283/document.
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Les travaux dont les résultats sont présentés dans ce manuscrit ont été menés dans le but de préparer des matériaux catalytiques à base de métaux nobles pour l'élimination de certains composés organiques volatils (COV). Différents catalyseurs à base de platine ont ainsi été préparés et leurs performances catalytiques évaluées pour l'oxydation de deux polluants : le n-butanol et l'acide acétique. Une première étude sur l'élimination oxydative et non-oxydative du n-butanol sur des catalyseurs à base de platine supportés sur alumine a été menée. Ce travail a porté essentiellement sur l'étude de l'effet des différents paramètres intervenant dans la réaction (oxygène, eau, métal). Le phénomène d'adsorption-désorption du polluant à la surface du catalyseur a également été étudié. S'inspirant des données de la littérature sur les propriétés redox particulières de la cérine, les travaux ont ensuite porté sur l'effet de l'ajout de CeO2 à des catalyseurs de type Pt/Al2O3 pour l'oxydation du n-butanol et de l'acide acétique. La modification des propriétés redox et acido-basiques ainsi que celle des performances catalytiques du matériau observées avec l'ajout de CeO2 a permis d'établir une corrélation entre activité catalytique en oxydation, capacité de stockage de l'oxygène et basicité. Cette corrélation a été confirmée dans la dernière étude menée sur des catalyseurs mis en forme de type monolithes enduits avec différents matériaux (Pt/Al2O3, Pt/CeO2, Pt/ZrO2, Pt/Al2O3-CeO2, Pt/Al2O3-ZrO2 et Pt/CeO2-ZrO2)The results presented in this manuscript have aimed at preparing catalytic materials based on noble metals for the removal of volatile organic compounds (VOC). Thus, different platinum based catalysts have been prepared and their catalytic performances have been evaluated for n-butanol and acetic acid oxidation. A first study on oxidative and non-oxidative removal of n-butanol over alumina supported platinum based catalysts has been performed. This work focused on the study of the effect of the different parameters involved in the reaction (oxygen, water, metal). The adsorption-desorption phenomenon of the pollutant on the catalyst surface has also been studied.Inspired by the literature on the specific redox properties of ceria, the work was then focused on the effect of the addition of CeO2 to Pt/Al2O3 catalysts for n-butanol and acetic acid oxidation. The modification of the redox and acid-base properties as well as that of the catalytic performances of the material with the addition of CeO2 allowed to establish a relationship between catalytic oxidation activities, oxygen storage capacity and basicity. This correlation has been confirmed in the last study performed on the monolithic catalysts coated with different materials (Pt/Al2O3, Pt/CeO2, Pt/ZrO2, Pt/Al2O3-CeO2, Pt/Al2O3-ZrO2 and Pt/CeO2-ZrO2)
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Barakat, Tarek. "Oxydation des composés organiques volatils en présence de catalyseurs Au et/ou Pd déposé sur TiO₂ nanostructuré dopé." Phd thesis, Université du Littoral Côte d'Opale, 2012. http://tel.archives-ouvertes.fr/tel-00916578.
Full textAbstract:
Dans ce travail, l'oxydation totale du toluène et de la butanone sur des catalyseurs à base d'or et de palladium supportés sur un oxyde de titane macro-mésoporeux a été étudiée. Nous avons tout d'abord discuté l'effet bénéfique du dopage (V, Nb, Fe, Ce, Ni) du support TiO₂ macro-mésoporeux sur l'activité catalytique de ce matériau. Une interaction existant entre le dopant et le support a joué un rôle important dans l'augmentation de l'activité des matériaux dopés par rapport à celle du titane pure. Une phase active constituée d'or et/ou de palladium a été ensuite déposée sur les solides dopés et la performance des catalyseurs préparés a été suivie dans l'oxydation du toluène et de la butanone. La présence de la phase active a assuré une sélectivité totale pour le CO₂ avec la formation de sous-produits en particulier dans l'oxydation de la butanone. Par ailleurs, l'oxydation du mélange des deux COVs a montré l'existence d'une compétition entre les molécules en terme d'adsorption sur le support, ce qui a favorisé leur éliminationà de basses températures. Une étude operando DRIFT réalisée dans l'oxydation du mélange toluène/butanone a vérifié la présence de cette compétition.
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Takky, Driss. "Effet de la structure moléculaire en electrocatalyse : étude mécanistique de l'oxydation des isomères du butanol en milieu aqueux sur diverses électrodes de metaux nobles." Poitiers, 1987. http://www.theses.fr/1987POIT2008.
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Brechot, Philippe. "Oxycarbonylation des olefines en presence de nitrites d'alkyle catalysee par les complexes du palladium." Paris 6, 1988. http://www.theses.fr/1988PA066107.
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Ali, Abdulkahhar. "Etudes electrochimique et chromatographique de la photooxydation des alcools primaires aliphatiques sur des suspensions de catalyseurs a base de dioxyde de titane." Poitiers, 1988. http://www.theses.fr/1988POIT2262.
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"The selective oxidation of n-butane to maleic anhydride." Thesis, 2003. http://hdl.handle.net/10413/3770.
Full textAbstract:
Industrial catalysts used in commercial processes for the production of maleic anhydride are mainly Vanadium Phosphorous Oxide (VPO) catalysts. The VPO catalyst used is Vanadyl Pyrophosphate (VO)2P207 made from its precursor Vanadium Phosphorous Hemi-Hydrate VOHP04.O.5H20 in an non-aqueous medium. In order for the VPO catalyst to perform optimally, a metal promoter, Ru, was
selected as the doping agent in this study. Four catalysts of different metal doping concentrations (undoped, 0.2%, 0.6% and 1%) were subjected to the oxidation of n-butane. Promoters are added to facilitate the oxidation of n-butane to maleic anhydride. n-Butane gas is now being used in many industrial processes, in fixed bed reactors to convert the gas to maleic anhydride. Catalysts were calcined under high temperatures under a nitrogen atmosphere. It was found that with an increase in reaction temperature, there was an increase in conversion of n-butane to maleic anhydride.
Selectivity of the product also showed an increase with an increase in temperature at a Gas Hourly Space Velocity (GHSV) of 1960-2170hr-1.
Catalysts were characterized using different techniques such as Electron Dispersive X-Ray Spectroscopy, Inductively Coupled Plasma-Atomic Emission Spectroscopy, Fourier Transform - Infra Red, Average Oxidation State, Brunauer Emmett and Teller (surface area), X-Ray Diffraction and Scanning Electron Microscopy. The 0.6% Ru
promoted VPO catalyst showed to be most effective in terms of conversion, selectivity and yield, at a temperature of 450°C as compared to the other catalysts studied. The catalysts degenerated after being subjected to higher temperatures. The selectivity obtained by this catalyst was at 70.2% and the yield obtained was 37%. This study showed that with an increase in Ru up to a certain concentration (0.6%), an increase in selectivity and yield was observed, thereafter, with additional Ru doping, a decrease in selectivity and yield was obtained.Thesis (M.Sc.)-University of Natal, 2003.
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Govender, Nishlan. "A comparative study of VPO catalysts in the oxidation of butane to maleic anhydride." Thesis, 2002. http://hdl.handle.net/10413/3791.
Full textAbstract:
Co promoted and unpromoted vanadium-phosphorous-oxide (VPO) catalysts were synthesized via an organic route. The catalyst precursor was calcined and then conditioned in a reactor, forming the
active vanadyl pyrophosphate, (VO)2P2O7, phase. Different promoter loaded catalysts were synthesized and their effect on the yield of maleic anhydride (MA) from n-butane oxidation was examined at different temperatures and gas hourly space velocities (GHSV). The catalysts were tested as a powder. The catalysts were examined in the oxidation of n-butane gas, over air as an oxidant, in a specially designed and constructed continuous flow, fixed-bed catalytic micro-reactor equipped with an on-line gas chromatography (GC) monitoring system. A thermal conductivity detector (TCD) was
employed for carbon oxide monitoring and a flame ionization detector (FID) for all other products. The catalysts were characterised by X-ray diffraction (XRD) to determine the phases present in the precursor, calcined and used catalysts. The Brunauer-Emmet-Teller (BET) surface area was calculated for the different promoter loaded catalysts. Fourier transform infrared (FT-IR) spectra, via the KBr
pellet method, and attenuated total reflectance (ATR) spectra were recorded to determine the anions present in the bulk and surface of the catalyst respectively. Energy dispersive X-ray (EDX) and inductively couple plasma-atomic emission spectroscopic (ICP-AES) techniques were employed to determine the elemental composition on the surface and in the bulk of the catalyst respectively. Scanning electron microscopic (SEM) images of the catalysts during different stages of their investigation were recorded. The average vanadium oxidation state (AV) in the bulk of the catalyst was determined via a titrimetric method. The catalysts were optimized to a high yield and selectivity of MA. The operating temperature, GHSV and promoter loading on the catalyst were the parameters that were changed during the testing of the catalyst. Different stages of the catalyst's life were characterised via the techniques mentioned above. The catalysts were monitored over a 200-hour period on average, usually taking approximately 24 hours to equilibrate. One such Co promoted
catalyst yielded 45 % MA at 275°C and GHSV of 2878 hr-1 on equilibration, with an n-butane conversion of 73 %, whilst all previously reported VPO catalysts produce far lower MA yields at this
temperature.Thesis (M.Sc.)-University of Natal, Durban, 2002.
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Ye, Yinmei. "Experimental study on n-Butane partial oxidation to maleic anhydride in a solid electrolyte membrane reactor = Experimentelle Untersuchung der partiellen Oxidation von n-Butanen zu Maleinsäureanhydrid in einem Festelektrolytmembranreaktor /." 2006. http://diglib.uni-magdeburg.de/Dissertationen/2006/yinye.htm.
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Ye, Yinmei [Verfasser]. "Experimental study on n-Butane partial oxidation to maleic anhydride in a solid electrolyte membrane reactor = Experimentielle Untersuchung der partiellen Oxidation von n-Butan zu Maleinsäureanhydrid in einem Festelektrolytmembranreaktor / von Yinmei Ye." 2006. http://d-nb.info/979547164/34.
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Liu, Hsin Yi, and 劉欣宜. "Hydrogen production by low temperature partial oxidation of butane over Ni-based catalysts modified by platinum." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/20928666575881686418.
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Huang, Wei-Chih, and 黃偉智. "Hydrogen-rich syngas production from bio-butanol by partial oxidation and oxidative steam reforming." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/04427276116786614238.
Full textAbstract:
碩士崑山科技大學
機械工程研究所
103
This study used the bio-butanol as the main fuel for reforming to produce hydrogen-rich synthesis gas. Two different reforming methods were adopted, including Partial Oxidation Reforming (POX) and Oxidation Steam Reforming (OSR). The theoretical equilibrium calculations were performed and compared with the experimantal results. Research is divided into two major parts, first one was to discuss the partial oxidation of butanol for hydrogen production and to identify the operation range of reforming; the second part is to investigate the synthesis of butanol oxidative steam reforming, and the parameters including hydrogen yield, conversion efficiency, reforming efficiency, and space velocity were investigated and analyzed. The results show that, firstly, the coke formation is almost close to zero by partial oxidation method under O2/C4H9OH molar ratio of 1.5, and the reaction temperature is above 700oC. Under different parameters in experiments, the maximum reforming range fell at the input fuel heating value of 1.5kW; and the best hydrogen concentration and yield of hydrogen was 30.6%, 81.98%, respectively; and the conversion efficiency of fuel and reforming efficiency was 94.57% and 76.85%, respectively. Then, from the theretical calculation on the oxidative steam reforming, the carbon deposition was depressed by the conditions of reaction temperature 600oC, O2/C4H9OH = 1.5 and S/C molar ratio over 3. With the parameters O2/C4H9OH = 1.5 and 2.0, S/C = 3 ~ 7, all experiments can reach the reaction temperature and have the widest reforming range. Under the operating conditions, hydrogen yield was 75.88%, the best conversion efficiency is 70.41% and reforming efficiency is 60.75%.
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Kah, Stefan. "Entwicklung und Einsatz von Mikrostrukturreaktoren mit katalytisch wirksamen Strömungskanälen für die partielle Gasphasen-Oxidation von 1-Buten." Doctoral thesis, 2004. https://monarch.qucosa.de/id/qucosa%3A18181.
Full textAbstract:
In der vorliegenden Arbeit wurden erstmalig Mikrostrukturreaktoren bei der partiellen Oxidation von 1-Buten zu Maleinsäureanhydrid (MSA) eingesetzt. Diese stark exotherme, heterogen katalysierte Umsetzung fand hierbei in Stapeln mikrostrukturierter Aluminiumfolien statt, welche durch parallele Strömungskanäle mit katalytisch wirksamen Oberflächenschichten charakterisiert sind. Als Aktivkomponenten kamen Vanadium-, Phosphor- und Titanoxide zur Anwendung. Ein Vergleich von drei kompakten Mikrostrukturreaktoren mit Kanaldurchmessern der Mikrokanäle von 0,08, 0,2 bzw. 0,4 mm mit einem Schüttgutreaktor wurde durchgeführt. Vorausgehend war die Entwicklung von 3 verschiedenen Methoden zur Immobilisierung von V2O5 und P2O5 auf dem Katalysatorträger bei jeweils unterschiedlichen Katalysatorvorläufern. Die Herstellungsparameter der geeignetsten Immobilisierungsmethode wurden, entsprechend einem Screening in Schüttgutreaktoren, systematisch variiert. Die katalytische Aktivierung der Folien erfolgte nach der gleichen Präparationsvorschrift die zur Herstellung des besten Katalysator-Schüttguts führte. Bei der partiellen Oxidation von 1-Buten außerhalb des Explosionsbereiches bestanden nur geringfügige Unterschiede zwischen den MSA-Selektivitäten im Schüttgut bzw. in der Mikrostruktur (33%). In letzterer wurden hingegen um den Faktor 3 bis 5 höhere Raum-Zeit-Ausbeuten als im Schüttgut erzielt. Des weiteren konnte die partielle Oxidation von 1-Buten innerhalb des Explosionsbereiches ausschließlich in den Mikrostrukturreaktoren explosionssicher - und ohne Anzeichen auf instabile Betriebspunkte gehandhabt werden. Begleitend dazu fand die Entwicklung und der Einsatz dreier modularer Mikrostrukturreaktoren bei der partiellen Oxidation von 1-Buten statt. Praktische Ergebnisse wurden anhand eines entwickelten Reaktormodells bestätigt.
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Bin, Hamzah Muhamad Firdaus. "Characteristics of Butanol Isomers Oxidation in a Micro Flow Reactor." Thesis, 2017. http://hdl.handle.net/10754/623480.
Full textAbstract:
Ignition and combustion characteristics of n-butanol/air, 2-butanol.air and isobutanol/air mixtures at stoichiometric (ϕ = 1) and lean (ϕ = 0.5) conditions were investigated in a micro flow reactor with a controlled temperature profile from 323 K to 1313 K, under atmospheric pressure.
Sole distinctive weak flame was observed for each mixture, with inlet fuel/air mixture velocity set low at 2 cm/s. One-dimensional computation with comprehensive chemistry and transport was conducted. At low mixture velocities, one-stage oxidation was confirmed from heat release rate profiles, which was broadly in agreement with the experimental results. The weak flame positions were congruent with literature describing reactivity of the butanol isomers. These weak flame responses were also found to mirror the trend in Anti-Knock Indexes of the butanol isomers.
Flux and sensitivity analyses were performed to investigate the fuel oxidation pathways at low and high temperatures. Further computational investigations on oxidation of butanol isomers at higher pressure of 5 atm indicated two-stage oxidation through the heat release rate profiles. Low temperature chemistry is accentuated in the region near the first weak cool flame for oxidation under higher
pressure, and its impact on key species – such as hydroxyl radical, hydrogen peroxide and carbon monoxide – were considered.
Both experimental and computational findings demonstrate the advantage of employing the micro flow reactor in investigating oxidation processes in the temperature region of interest along the reactor channel. By varying physical conditions such as pressure, the micro flow reactor system is proven to be highly beneficial in elucidating oxidation behavior of butanol isomers in conditions in engines such as those that mirror HCCI operations.
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Majoe, Nampe. "Oxidative dyhydrogenation of propane and butane to olefins using Co(5)MgA/O catalyst." Diss., 2019. http://hdl.handle.net/10500/26365.
Full textAbstract:
Olefins have enjoyed many uses in a wide variety of industries, from car manufacturing to energy production. Energy consuming processes of catalytic dehydrogenation, turning paraffins into olefins, has been commercialised since the early 20th century, while catalytic oxydehydrogenation of paraffins to olefins is still in prototype stages. The conflict between kinetic and thermodynamic yield constraints, has delayed the commercialisation of this process. The solution to achieving the relevant process route is exploitation of the right catalyst at moderate temperatures and pressures. Co5MgAlO is studied under atmospheric pressure and 350°C temperature, to dehydrogenate propane and butane to olefins using oxygen as a reactant. Thermodynamic models showing how many reaction routes are possible under atmospheric pressure were explored. Experimental results for butane to air at ratio of 1:0.8 and 1:1.2 hydrocarbons to air gave better selectivity of 1-butene which was more than 12%. When compared with propane at similar reaction ratios the reaction favoured CO2 at selectivity of more than 95%.Civil and Chemical Engineering
M.Tech. (Chemical Engineering)
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PARK, TAE-JIN. "OXIDATIVE DEHYDROGENATION OF BUTENES OVER ZINC-FERRITE CATALYSTS." Thesis, 1987. http://hdl.handle.net/1911/16101.
Full textAbstract:
The oxidative dehydrogenation (OXD) of butene over a zinc ferrite catalyst was studied in a batch recirculation and microcatalytic pulse reactor system at temperatures between 300 and 400$\sp\circ$C. Mechanistic features of the reaction were examined using deuterium labeled butene and $\sp{18}$O-labeled carbon dioxide experiments. Solid state changes in the catalyst were examined through x-ray powder diffraction and Mossbauer spectroscopy.
Reaction products consist of 1,3-butadiene, carbon dioxide, water, and butene isomers. At higher reaction temperatures, a small amount of carbon monoxide was observed. Kinetic expressions were constructed for both OXD and deep oxidation reactions based on a two site Langmuir-Hinshelwood model assuming dissociative adsorption for oxygen on one site and competitive adsorption by butene and butadiene on the other. Preliminary values for the kinetic parameters were evaluated from initial reaction rate data and were refined to fit the integral data obtained as a function of time. The activation energies for OXD and deep oxidation are 34.1 and 30.6 Kcal/mole, respectively.
The OXD of perdeuterated butene is slower than that of undeuterated butene, which indicates a significant kinetic isotope effect of 2.7 at 350$\sp\circ$C. A similar effect was observed for isomerization of cis-2-butene to 1-butene by double bond shift (1.4 at 350$\sp\circ$C). Apparently, carbon-hydrogen bond cleavage is involved in the rate limiting step for both reactions.
Microcatalytic pulse experiments carried out in the absence of gas phase oxygen indicated that the lattice oxygen does not participate in the reaction and that the migration of bulk oxygen to the surface of the catalyst is very slow under these conditions. A similar result was observed in $\sp{18}$O exchange experiments with C$\sp{18}$O$\sb 2$.
The experimental data are consistent with an oxidation-reduction cycle involving Fe$\sp{+2}$/Fe$\sp{+3}$ interconversion. Butene and oxygen molecules may adsorb into surface anion vacancies associated with an iron cation. The absence of intermolecular hydrogen-deuterium exchange during the isotopic tracer experiments indicates that the OXD and isomerization reaction rates are much greater than surface diffusion of hydrogen and/or deuterium.
The catalytic activity of zinc ferrite increases greatly when it is exposed to a high temperature under the reaction environment. Solid state studies using x-ray diffraction and Mossbauer spectroscopy indicated that the zinc ferrite phase decomposes into zinc oxide and iron oxides. Iron oxides thus formed are considered to be responsible for the enhancement of the catalytic activity.
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Milne, Alan David. "The application of the attainable region concept to the oxidative dehyrogenation of N-butanes in inert porous membrane reactors." Thesis, 2009. http://hdl.handle.net/10539/6871.
Full textAbstract:
The availability of kinetic data for the oxidative dehydrogenation (ODH) of
n-butane from Téllez et al. (1999a and 1999b) and Assabumrungrat et al.
(2002) presented an opportunity to submit a chemical process of industrial
significance to Attainable Region (AR) analysis.
The process thermodynamics for the ODH of n-butane and 1-butene have
been reviewed. The addition of oxygen in less than the stoichiometric ratios
was found to be essential to prevent deep oxidation of hydrocarbon products
{Milne et al. (2004 and 2006c)}.
The AR concept has been used to determine the maximum product yields
from the ODH of n-butane and 1-butene under two control régimes, one
where the partial pressure of oxygen along the length of the reactor was
maintained at a constant level and the second where the oxygen partial
pressure was allowed to wane. Theoretical maxima under the first régime
were associated with very large and impractical residence times.
The Recursive Convex Control policy {Seodigeng (2006)} and the second
régime were applied to confirm these maxima {Milne et al. (2008)}. Lower
and more practical residence times ensued. A differential side-stream reactor
was the preferred reactor configuration as was postulated by Feinberg
(2000a).
Abstract
A.D. Milne Page 4 of 430
The maximum yield of hydrocarbon product, the associated residence time
and the required reactor configuration as functions of oxygen partial
pressure were investigated for the series combinations of an inert porous
membrane reactor and a fixed-bed reactor. The range of oxygen partial
pressures was from 85 kPa to 0.25 kPa. The geometric profile for
hydrocarbon reactant and product influences the residence times for the
series reactors.
The concept of a residence time ratio is introduced to identify the operating
circumstances under which it becomes advantageous to select an inert
membrane reactor in preference to a continuously stirred tank reactor and
vice versa from the perspective of minimising the overall residence time for
a reaction {Milne et al. (2006b)}.
A two-dimensional graphical analytical technique is advocated to examine
and balance the interplay between feed conditions, required product yields
and residence times in the design of a reactor {Milne et al. (2006a)}..
A simple graphical technique is demonstrated to identify the point in a
reaction at which the selectivity of the feed relative to a product is a
maximum {Milne et al. (2006a)}.
Literature Cited
Assabumrungrat, S. Rienchalanusarn, T. Praserthdam, P. and Goto, S.
(2002) Theoretical study of the application of porous membrane reactor to
Abstract
A.D. Milne Page 5 of 430
oxidative dehydrogenation of n-butane, Chemical Engineering Journal,
vol. 85, pp. 69-79.
Feinberg, M. (2000a) Optimal reactor design from a geometric viewpoint –
Part II. Critical side stream reactors, Chemical Engineering Science, vol. 55,
pp. 2455-2479.
Milne, D., Glasser, D., Hildebrandt, D., Hausberger, B., (2004), Application
of the Attainable Region Concept to the Oxidative Dehydrogenation of 1-
Butene in Inert Porous Membrane Reactors, Industrial and. Engineering
Chemistry Research, vol. 43, pp. 1827-1831 with corrections subsequently
published in Industrial and Engineering Chemistry Research, vol. 43,
p. 7208.
Milne, D., Glasser, D., Hildebrandt, D., Hausberger, B., (2006a), Graphical
Technique for Assessing a Reactor’s Characteristics, Chemical Engineering
Progress, vol. 102, no. 3, pp. 46-51.
Milne, D., Glasser, D., Hildebrandt, D., Hausberger, B., (2006b), Reactor
Selection : Plug Flow or Continuously Stirred Tank?, Chemical Engineering
Progress. vol. 102, no. 4, pp. 34-37.
Milne, D., Glasser, D., Hildebrandt, D., Hausberger, B., (2006c), The
Oxidative Dehydrogenation of n-Butane in a Fixed Bed Reactor and in an
Inert Porous Membrane Reactor - Maximising the Production of Butenes
and Butadiene, Industrial and Engineering Chemistry Research vol. 45,
pp. 2661-2671.
Abstract
A.D. Milne Page 6 of 430
Milne, D., Seodigeng, T., Glasser, D., Hildebrandt, D., Hausberger, B.,
(2008), The Application of the Recursive Convex Control (RCC) policy to
the Oxidative Dehydrogenation of n-Butane and 1-Butene, Industrial and
Engineering Chemistry Research, (submitted for publication).
Seodigeng, T.G. (2006), Numerical Formulations for Attainable Region
Analysis, Ph.D. thesis, University of the Witwatersrand, Johannesburg,
South Africa.
Téllez, C. Menéndez, M. Santamaría, J. (1999a) Kinetic study of the
oxidative dehydrogenation of butane on V/MgO catalysts, Journal of
Catalysis, vol. 183, pp. 210-221.
Téllez, C. Menéndez, M. Santamaría, J. (1999b) Simulation of an inert
membrane reactor for the oxidative dehydrogenation of butane, Chemical
Engineering Science, vol. 54, pp. 2917-2925.
__________________________________
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Herberth, Edith. "Hydro- und Carboborierungs-/Oxidationsreaktionen von Tricyclo[4.1.0.02,7]heptan-Derivaten sowie Synthese und Solvolyse-Reaktionen von exo,exo-Bicyclo[1.1.0]butan-2,4-dimethanoldimethansulfonat." Doctoral thesis, 2002. https://nbn-resolving.org/urn:nbn:de:bvb:20-opus-4952.
Full textAbstract:
Die bekannte Umwandlung des Bromtricycloheptans 4 in den Homoallylalkohol 76 durch Hydroborierung/Oxidation wurde anders als früher mit einer in situ aus Natriumborhydrid und elementarem Iod erzeugten Boran-THF-Lösung bewirkt. Darüber hinaus konnten unter den gleichen Bedingungen das Chlortricycloheptan 26 und das Methyltricycloheptan 62 in den Homoallylalkohol 108 bzw. 109 überführt werden. Über 4, 26, 62 und das Phenyltricycloheptan 15 hinaus, dessen Hydroborierung/ Oxidation zum Homoallylalkohol 45a schon früher gelungen war, wurde eine Reihe von Bicyclo[1.1.0]butan-Derivaten mit Boran behandelt und das Gemisch dann oxidiert. Allerdings ergab sich in keinem Fall ein zu den Homoallylalkoholen 45a, 76, 108 und 109 analoges Produkt. Über die Ursachen dieser Misserfolge kann gegenwärtig nur spekuliert werden. Immerhin fand sich bei 3,4-Benzotricyclo[4.1.0.02,7]heptan (83) ein Hinweis auf eine Oligomerenbildung des Substrats. Als Grund für die Anlagerung von Boran an 4, 15, 26 und 62 wird die Fähigkeit der Substituenten am Tricycloheptan-System, eine positive Ladung zu stabilisieren, gesehen. Durch die Umsetzung von Trideuteroboran mit 4 wurden bestimmte Reaktions-mechanismen ausgeschlossen, etwa der via das Umlagerungsprodukt 119 von 4 und Hydroborierung von 119, und der mit dem Zwitterion 120 gestützt, das durch 1,2-Deuteridverschiebung in das Cyclohexenylmethylboran 121 umlagern sollte, das als die Vorstufe des nach der Oxidation isolierten Produkts 87 angesprochen wird. Die Reaktionen von 4 und 15 mit 9-Borabicyclo[3.3.1]nonan (9-BBN), gefolgt von der Oxidation des Gemisches, lieferten je nach der Geschwindigkeit der Zugabe von 9-BBN entweder die Dialkohole 122 bzw. 123, jeweils als Diastereomerengemische, oder/und die Homoallylalkohole 76 bzw. 45a. Als Vorstufen der Verbindungen 122 und 123 werden Zwitterionen des Typs 124, Trialkylborane 125, Zwitterionen 127 und Trialkylborane 128 und 129 gesehen. Die Zwitterionen 124 sollten durch Addition von 9-BBN an die Substrate 4 und 15 entstehen und durch Hydridwanderung in 125 übergehen, deren Anlagerung von 4/15 die Zwitterionen 126 und dann 127 hervorbringen sollte. Die 1,2-Wanderung eines Achtring-Kohlenstoffatoms müsste zu 128 und 129 führen, die durch Oxidation in 122/123 umgewandelt werden dürften. Das Dimesylat exo,exo-142 wurde in einer mehrstufigen Synthese über den bekannten Dibromdialkohol 148 ausgehend von Benzvalen (82) synthetisiert. Die Alkoholfunktionen von 148 wurden mit Trimethylsilylchlorid geschützt unter Bildung des Bis(silylethers) 151. Aus 151 wurde durch Umsetzung mit tert-Butyllithium das Bicyclobutan exo,exo-152 dargestellt. Nach Abspaltung der Schutzgruppen mit Kaliumcarbonat in Methanol wurde der Dialkohol exo,exo-150 erhalten, welcher mit Methansulfonsäurechlorid zum Zielmolekül exo,exo-142 reagierte. Die Reaktion einer 2:1-Mischung aus exo,exo-150 und 157 mit Natriumhydrid und Iodethan lieferte die Bis(ethylether) 160 und 161 in 38% bzw. 19% Ausbeute. In den Solvolyse-Reaktionen wurde ein 36:1:16-Gemisch aus exo,exo-142, endo,-endo-142 und 159 eingesetzt. Bei der Reaktion des Gemischs in 60% wässrigem Aceton in Gegenwart von Triethylamin bei 40 °C über fünf Tage zeigten die NMR-Spektren die Abnahme von exo,exo-142 um 75% (bezogen auf 159 als internen Standard), es konnte aber kein Produkt identifiziert werden. Die Ethanolyse bei 40 °C in Gegenwart von Triethylamin lieferte nach drei Tagen ein 3.5:2.8:1.0-Gemisch aus exo,exo-142, 159 und 162. Die Verbindung 162 wurde mit 70% Ausbeute (bezogen auf umgesetztes exo,exo-142) gebildet. Die NMR-Spektren zeigten einen Umsatz von exo,exo-142 von 30% (bezogen auf 159 als internen Standard). Wurde die Reaktion unter den gleichen Bedingungen sieben Tage durchgeführt, verringerte sich der Anteil an exo,exo-142 um 50% und man erhielt eine 1:1:1-Mischung aus exo,exo-142, 159 und 162. Die Ausbeute von 162 lag bei 50% (bezogen auf umgesetztes exo,exo-142). Bei der Solvolyse in 2,2,2-Trifluorethanol über drei Tage bei 40 °C in Gegenwart von Triethylamin erhielt man ein 3.2:2.0:1.0-Gemisch aus exo,exo-142, 159 und 163. Anhand der NMR-Spektren wurde ein Umsatz von exo,exo-142 von 20% beobachtet (bezogen auf 159 als internen Standard). Die Solvolyse-Reaktionen des Dimesylats exo,exo-142 verlaufen, anders als die seines Diastereomers endo,endo-142, unter ausschließlicher Bildung von Produkten mit nicht umgelagertem Gerüst und liefern damit erstmals einen deutlichen Hinweis für die Existenz eines Bicyclo[1.1.0]but-2-exo-ylcarbinyl-Kations (166) als Intermediat. Es ist zu erwarten, dass 162 und 163 ihrerseits solvolysieren unter Bildung des Bis(ethylethers) 160 bzw. dessen Hexafluor-Derivates, aber diese Verbindungen sind unter den Solvolysebedingungen nicht stabil. Dies konnte in einem Kontrollexperiment bestätigt werdenThe known transformation of bromotricycloheptane 4 into the homoallylalcohol 76 by hydroboration/oxidation was performed different to the earlier procedure by using in the first step a THF solution of borane generated in situ from sodiumborohydride and elemental iodine. Furthermore chlorotricycloheptane 26 and methyltricycloheptane 62 could be transformed into the homoallylalcohol 108 and 109, respectively, by using the same reaction conditions. Beside 4, 26, 62 and phenyltricycloheptane 15, which hydroboration/oxidation to homoallylalcohol 45a succeeded earlier, a variety of bicyclo[1.1.0]butane derivatives was treated with borane and then the mixture was oxidized. But no reaction resulted in a product analogous to the homoallylalcohols 45a, 76, 108 and 109. About the reason for the failure of these reactions at this time only can be speculated. However, in the case of 3,4-benzotricyclo[4.1.0.02,7]heptane (83) evidence was given for formation of oligomers from the substrate. The ability to stabilize a positive charge of the substituents at the tricycloheptane system is to be considered as a reason for the addition of borane to 4, 15, 26 and 62. Based on the transformation of 4 with trideuteroborane certain reaction mechanisms, for example that via the rearrangement product 119 of 4 and hydroboration of 119, were excluded and that with the zwitterion 120 was supported. 120 should rearrange through a 1,2-shift of deuteride into cyclohexenylmethylborane 121 which is seen as a precursor in the oxidation reaction to the isolated product 87. The reactions of 4 and 15 with 9-borabicyclo[3.3.1]nonane (9-BBN) followed by oxidation of the mixture generated depending on the addition rate of 9-BBN to the substrate the dialcohols 122 and 123, respectively, in both cases as a diastereomeric mixture and/or the homoallylalcohol 76 and 45a, respectively. Zwitterions 124, trialkylboranes 125, zwitterions 127 and trialkylboranes 128 and 129 are considered as precursors for the compounds 122 and 123. The zwitterions 124 should be formed by addition of 9-BBN to the substrates 4 and 15 and should be transformed by hydride shift into 125 which should give rise to zwitterions 126 and then 127 after addition of 4/15. 1,2-Shift of a carbon atom of the eight-membered ring should lead to 128 and 129 which should be transformed into 122/123 by oxidation. Dimesylate exo,exo-142 was obtained in a more step reaction via the known dibromodialcohol 148 starting from benzvalene (82). The alcohol groups of 148 were protected with trimethylsilyl chloride by formation of the bis(silyl ether) 151. Bicyclo-butane exo,exo-152 was obtained from 151 by reaction with tert-butyllithium. After removing the protecting groups with potassium carbonate in methanol the dialcohol exo,exo-150 was formed. This alcohol reacted with methanesulfonyl chloride to the target molecule exo,exo-142. The reaction of a 2:1 mixture of exo,exo-150 and 157 with sodium hydride and iodoethane generated the bis(silyl ethers) 160 and 161 in 38% and 19% yield, respectively. For the solvolyses reactions a 36:1:16 mixture of exo,exo-142, endo,endo-142 and 159 was used. After reacting the mixture in 60% acetone/water in the presence of triethylamine at 40 °C during five days the NMR spectra showed a decrease of exo,exo-142 by 75% (determined by using 159 as internal standard) while no product could be identified. The ethanolysis at 40 °C during three days in the presence of triethylamine produced a 3.5:2.8:1.0 mixture of exo,exo-142, 159 and 162. The compound 162 was formed with 70% yield (based on exo,exo-142 consumed). The NMR spectra showed that the proportion of exo,exo-142 had decreased by 30% (determined by using 159 as internal standard). After seven days using the same reaction conditions the proportion of exo,exo-142 decreased by 50% (determined by using 159 as internal standard) and a 1:1:1 mixture of exo,exo-142, 159 and 162 was obtained. 162 was formed with 50% yield (based on exo,exo-142 consumed). Solvolysis in 2,2,2-trifluoroethanol at 40 °C during three days in the presence of triethylamine produced a 3.2:2.0:1.0 mixture of exo,exo-142, 159 und 163. In the NMR spectra a decrease of exo,exo-142 by 20% was observed (determined by using 159 as internal standard). The solvolyses reactions of the dimesylate exo,exo-142 proceed, in contrast to those of its diastereomer endo,endo-142, solely with formation of unrearranged products and therefore they offer for the first time strong evidence for the intermediacy of a bicyclo[1.1.0]-but-2-exo-ylcarbinyl cation (166). It should be expected that the compounds 162 and 163 solvolyses on their part to give the bis(ethyl ether) 160 and its hexafluoro-derivative, respectively, but these compounds are not stable under the solvolyses conditions. This was proved by a control experiment
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YIN, CHIEN-REN JOE. "OXIDATIVE DEHYDROGENATION OF BUTENES OVER TIN-PHOSPHORUS-OXYGEN AND LITHIUM-TIN-PHOSPHORUS - OXYGEN CATALYSTS." Thesis, 1987. http://hdl.handle.net/1911/16117.
Full textAbstract:
The mechanism of catalytic oxidative dehydrogenation (OXD) of butenes to 1,3-butadiene over Sn-P-O and Li-Sn-P-O catalysts was investigated in batch recirculation and microcatalytic pulse reactors. Mechanistic features of the reaction were examined using deuterium labeled butene (isotopic tracer technique) and $\sp{18}$O-labeled carbon dioxide (oxygen isotope exchange) experiments. Solid state changes in the catalyst were examined through BET surface area, electron microscopy, x-ray powder diffraction, and x-ray photoelectron spectroscopy.
Reaction products include 1,3-butadiene, carbon dioxide, water, and butene isomers.Both Sn-P-O and Li-Sn-P-O catalysts have activity of about 11% conversion and about 98% initial selectivity for butadiene after 15 minutes reaction time at 300$\sp\circ$C. Catalyst deactivation is caused by the formation of coke, which decreases the catalyst surface area. The Sn-P-O catalyst forms coke more readily than the Li-Sn-P-O catalyst. The activity of the aged catalysts can be partially recovered with treatment in 150 torr oxygen at 500$\sp\circ$C.
The rate of formation of butadiene is zero order in both oxygen and butene. The rate of formation of carbon dioxide is zero order in butene and about 0.5 order in oxygen. The OXD reaction is inhibited by product butadiene, where low conversion data can be modeled by a modified Langmuir-Hinshelwood type rate expression. But the rate expression does not fit CO$\sb 2$ well. The activation energy for butadiene formation is about 19 kcal/mole over the Li-Sn-P-O catalyst.
Microcatalytic pulse experiments carried out in the absence of gas phase oxygen indicated that the reactions probably proceed by consuming catalyst surface oxygen. Two consecutive sets of $\sp{18}$O labeled CO$\sb 2$ pulse experiments demonstrate that only surface oxygen is relatively mobile, and that bulk diffusion of oxygen to the surface may not play a very important role in the OXD mechanisms. Perdeuterated butene is less reactive than non-deuterated butene. Comparison of the rates of formation and analysis of isotopic compositions of the products revealed a significant kinetic isotopic effect for the OXD reaction. Therefore, carbon-hydrogen bond cleavage is considered rate limiting.
Isomerization may occur via a concurrent non-oxidative reaction over weak acid sites. Experimental data are consistent with an oxidation-reduction cycle involving a Sn$\sp{+4}$ cation active center.
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廖心慈. "Kinetics of direct and oxidative dehydrogenation of n-Butanol over Ba O-CuO/SiO��." Thesis, 1989. http://ndltd.ncl.edu.tw/handle/97900860287975403871.
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Gupta, Neeraj. "DNA oxidation and base excision repair in lung and liver of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone treated mice." Thesis, 2011. http://hdl.handle.net/1974/6465.
Full textAbstract:
4-(Methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) is a potent pulmonary carcinogen found in unburned tobacco and tobacco smoke. To exert its carcinogenic effect, NNK is metabolically activated to reactive intermediates that can damage DNA by alkylation or pyridyloxobutylation. NNK also has the ability to induce DNA oxidation and alter DNA repair activities that can result in deficient repair and potentially exacerbate carcinogenesis. Base excision repair (BER) is a ubiquitous DNA repair system that mainly repairs oxidative DNA damage. The goal of this study was to determine the effect of NNK on DNA oxidation status and BER activity in A/J mouse lung and liver. Female mice were treated with 10 µmol of NNK i.p. and lung and liver were isolated 1, 2 and 24 hours post administration. DNA was isolated from lung and liver, and the formation of 8-hydroxydeoxyguanosine (8-OHdG, a biomarker of DNA oxidation) was assessed by high-performance liquid chromatography with electrochemical detection. At 1, 2 and 24 hours in both murine lung and liver, there was no statistically significant difference in 8-OHdG levels (n = 4, P > 0.05) between control and NNK-treated mice. To assess BER, cell-free whole tissue nuclear protein extracts from liver and lung were prepared and incubated with a plasmid substrate containing oxidative DNA damage. In vivo treatment with NNK did not alter BER activity in lung or liver compared to control mice (n=3 or 4, P > 0.05). These experiments indicate that acute treatment with a tumourigenic dose of NNK does not significantly stimulate oxidative DNA damage or significantly alter BER activity in murine lung and liver.Thesis (Master, Pharmacology & Toxicology) -- Queen's University, 2011-04-28 17:42:08.172
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Kah, Stefan [Verfasser]. "Entwicklung und Einsatz von Mikrostrukturreaktoren mit katalytisch wirksamen Strömungskanälen für die partielle Gasphasen-Oxidation von 1-Buten / vorgelegt von Stefan Kah." 2004. http://d-nb.info/975645501/34.
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Grajales, Gonzalez Edwing. "Theoretical Kinetic Study of the Unimolecular and H-Assisted Keto-Enol Tautomerism Propen-2-ol ↔Acetone. Pressure Effects and Implications in the Pyrolysis and Oxidation of tert- And 2-Butanol." Thesis, 2018. http://hdl.handle.net/10754/627914.
Full textAbstract:
The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with their favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular and H-assisted tautomerism of propen-2-ol to acetone, which are included in butanol combustion kinetic models, are assigned rate parameters based on the analogous unimolecular tautomerism vinyl alcohol ↔ acetaldehyde and H addition to the double bound of iso-butene, respectively. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the unimolecular and H-assisted tautomerism, i-C3H5OH⟺CH3COCH3 and i-C3H5OH+Ḣ⟺CH3COCH3+Ḣ, was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) and CCSD(T)/aug-cc-pVTZ//M062X/cc-pVTZ ab initio calculations, respectively. For H-assisted tautomerism, the reaction takes place in two consecutive steps: i-C3H5OH+Ḣ⟺CH3ĊOHCH3 and CH3ĊOHCH3⟺CH3COCH3+Ḣ. Multistructural torsional anharmonicity and variational transition state theory were considered in a wide temperature and pressure range (200 K – 3000 K, 0.1 kPa – 108 kPa). It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior for both isomerizations.
Results for unimolecular tautomerism differ from vinyl alcohol ↔ acetaldehyde analogue reactions, which shows lower rate constant values. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed unimolecular rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption.
In the combustion and pyrolysis batch reactor simulations, using all the rate constants computed in this work, H-assisted reactions are limited because H radicals become abundant once the propen-2-ol has been consumed by other reactions, such as the non-catalyzed tautomerism i-C3H5OH⟺CH3COCH3, which becomes one of the main source of acetone. The intermediate radical (CH3ĊOHCH3) is formed exclusively from tert-butanol, with its concentration in 2-butanol oxidation being smaller because the secondary alcohol is unable to produce the radical directly. In all cases, the intermediate is converted effectively to acetone.