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Dissertations / Theses on the topic 'Butene'

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Published: 4 June 2021
Last updated: 15 June 2025

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1

Hub, Serge. "Mecanismes d'hydrogenation des butene-1 et butyne-1 sur catalyseurs au palladium." Université Louis Pasteur (Strasbourg) (1971-2008), 1986. http://www.theses.fr/1986STR13325.

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2

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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3

Cullen, Bernard. "Selective hydrogenation of a multifunctional compound : 2-butyne-1,4-diol to cis-2-butene-1,4-diol." Thesis, University of Glasgow, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.412969.

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4

Bruhn, Timm. "Rotationsspektroskopische und quantenchemische Studien zur Methyltorsion in halogenierten Dimethylethenen." [S.l.] : [s.n.], 2000. http://deposit.ddb.de/cgi-bin/dokserv?idn=962671681.

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5

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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6

Stefanowicz-Pieta, Izabela. "1-butene isomerisation over silica-alumina catalyst." Thesis, University of Aberdeen, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.487424.

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Reactions involving double-bond and skeletal isomerization of alkenes have been widely investigated, however, the relations between the activity and selectivity and strength or density of the acid sites are still not fully understood. Most authors believe that the reaction is catalysed by Bmnsted acid sites while others support the idea that Lewis sites can act in this reaction and discussion still exists as to the exact role of carbonaceous materials and of dimeric/ oligomeric intermediates. The double-bond isomerization of n-butene has been studied previously and it seems that an apparent correlation exists between selectivity and acidity or basicity of the catalyst. This reaction is considered to take place through a carboanionic or carbocationic mechanism. However until now the subject of surface acidity/basicity and its correlation with catalytic activity and also the mechanism of double bond isomerization reaction is still under debate. In order to investi~ate the correlation between activity and surface acidity silica-alumina catalysts were calcined at a range of temperature 300-550 °c in order to produce a series of samples with different Bmnsted and Lewis acid site densities. The numbe~ of acid sites was measured by combined FTIR/gravimetric measurements from the adsorption of2,6 and 2,4lutidine and pyridine. For each catalyst, a cycle of I-butene isomerization reactions was carried out. Reactions were performed using a fixed bed reactor under a constant flow of I ml/min of I-butene in total flow of the gases 100 ml/min. The only products of this reaction were cis-butene and trans-butene. This study indicates that amorphous silica-alumina is an active catalyst for double bond isomerization. In agreement with previously studies, no dimerization, oligomerization, coke or by-product formation was found under the reaction conditions selected. However deactivation is observed especially during the first 50 min of the reaction. The calculated activation energy of cis-butene formation was 48±5 kJ morl consistent with values reported in the literature. The work presented aims at establishing a relationships between the type, or types of acidity and number of sites, with the activity in the isomerisation reaction.
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7

Agulló, Pastor Javier. "1-butene isomerisation over amorphous silica-alumina." Thesis, University of Aberdeen, 2012. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?pid=189659.

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The dehydroxylation process of pseudo-boehmite to yield acidic amorphous silica-alumina has been investigated by increasing the temperature of the sample and recording DRIFTS spectra of its surface and monitoring the water released with an on-line mass spectrometer. The Brønsted and Lewis acid sites density of amorphous silica-alumina has been determined by IR-spectrometry of adsorbed pyridine and using molar extinction coefficients specific for this system for silica-alumina samples calcined at different temperatures. The deactivation profiles of 1-butene isomerisation (double-bond migration) over amorphous silica-alumina samples calcined at different temperatures have been acquired by using a fixed bed laboratory reactor coupled to a gas chromatograph with an automated sampling valve. The initial activities of amorphous silica-alumina calcined at different temperatures correlated with the Brønsted acid site density of the samples. The deactivation profiles are consistent with a reversible rehydration deactivation mechanism involving both Brønsted and Lewis acid sites and simultaneous to an irreversible deactivation mechanism involving Lewis acid sites. Brønsted acid sites are considered to be the active sites of the reaction, whereas part of the Lewis acid sites is converted into Brønsted acid sites by rehydration.
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8

Harmse, Liesel. "Improvement of propylene yield via butene metathesis." Master's thesis, University of Cape Town, 2008. http://hdl.handle.net/11427/5323.

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Includes synopsis.<br>Includes bibliographical references (leaves [96]-100).<br>There is an increasing interest in finding ways to produce on-purpose propene, due to the significant predicted propene growth in the next few years without the concomitant growth in the ethene demand, One of the technologies available is 1-butene metathesis, which describes a one-step process where isomerisation of 1-butene to 2-butene followed by cross-metathesis taking place. Products of the cross metathesis are propene and 2-pentene. In addition ethene and 3-hexene are expected as products of 1-butene metathesis.
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9

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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10

Shen, Wei. "Alkylation of isobutane/1-butene over acid functionalized mesoporous materials." Thesis, Université Laval, 2010. http://www.theses.ulaval.ca/2010/27073/27073.pdf.

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11

Wuchter, Nils. "Hydrierung von 1,3-Butadien und Hydroisomerisierung der Folgeprodukte n-Butene an Pd-Al2O3-Schalenkatalysatoren." Phd thesis, [S.l. : s.n.], 2000. http://elib.tu-darmstadt.de/diss/000056.

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12

Zuazo, Iker. "Deactivation routes in zeolite catalyzed isobutane/2-butene alkylation and regeneration procedures." [S.l. : s.n.], 2004. http://deposit.ddb.de/cgi-bin/dokserv?idn=97204227X.

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13

Haskins, Geoff D. "Reactor modifications for ethylene-butene gas-phase copolymerization." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape8/PQDD_0001/MQ42626.pdf.

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14

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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15

Platon, Alexandru. "Characterization of solid acid catalysts for isobutane/butene alkylation." Online access for everyone, 2004. http://www.dissertations.wsu.edu/Dissertations/Fall2004/a%5Fplaton%5F100104.pdf.

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16

Mulder, Mark Henry. "Solubility of ethylene, 1-butene and 1-hexene in polyethylenes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape8/PQDD_0020/MQ47073.pdf.

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17

Shaw, Jeremy P. "The processing, structure and properties of poly(1-butene) monofilaments." Thesis, Loughborough University, 1987. https://dspace.lboro.ac.uk/2134/32074.

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An investigation into the structure and properties of poly(1-butene) monofilaments was carried out. Eight commercial grades of poly(1-butene) were thoroughly characterized and compared by a wide range of techniques: DSC, GPC, C13nmr, melt rheology, optical and electron microscopy, crystallization rates and crystallinity were also measured. Both qualitative and quantitative information was obtained on additives, blends, copolymers and polymer tacticity. To compare the mechanical properties of the materials in the absence of molecular orientation at various levels of crystallinity compression moulded sheets were produced.
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18

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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19

Demolis, Alexandre. "Synthèse catalytique de lévulinates de butyle à partir de biomasse en présence d’alcools ou d’oléfines." Thesis, Lyon, 2016. http://www.theses.fr/2016LYSE1180/document.

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L'objectif de ce travail était d'étudier en profondeur la synthèse catalytique de lévulinates de butyle à partir de biomasse, d'abord en utilisant les isomères de butanol, puis les isomères de butène comme agents d'estérification. Généralement obtenus par estérification de l'acide lévulinique, les esters lévuliniques et notamment les lévulinates de butyle présentent des propriétés physiques et chimiques faisant d'eux de potentiels additifs de carburant, molécules plateformes, solvants ou encore additifs pour l'industrie alimentaire ou pharmaceutique. En convertissant sélectivement la cellulose en lévulinates de butyle, aucune étape de synthèse et de purification d'intermédiaires réactionnels n'a été nécessaire. Dans les isomères de butanol, la conversion de la cellulose en lévulinates avec H2SO4 a permis d'obtenir à 200°C respectivement 50 et 14% d'esters dans les alcools primaires et secondaire. L'utilisation de zircone sulfatée et de phosphotungstate de césium a abouti à la formation de 15% d'esters dans les alcools primaires, et de 3% dans l'alcool secondaire. L'utilisation d'oléfines comme substituant aux alcools fut étudiée en présence d'acide sulfurique. Avec le n-butène, l'estérification de l'acide lévulinique a donné 55% de lévulinate de sec-butyle à 100°C et en absence de solvant. A partir de cellulose, un rendement de 19% a été obtenu à 100°C dans l'iso-octane. Avec l'iso-butène, 50% de lévulinate de tert-butyle ont été obtenus à partir de l'acide lévulinique, sans solvant et à 25°C. En présence d'Amberlyst-15, 80% de rendement ont pu être obtenus, avec une réutilisation jusqu'à 6 fois du catalyseur sans désactivation notable<br>The objective of this work was to study in details the catalytic synthesis of butyl levulinates from biomass, first by using butanol isomers, then butene isomers as esterifying agents. Usually obtained by esterification of levulinic acid, levulinic esters including butyl levulinates possess physical and chemical properties making them potential fuel additives, platform molecules, solvents or additives for the food or pharmaceutical industry. By selectively converting cellulose into butyl levulinates, no step of synthesis and purification of reaction intermediates was necessary. In butanol isomers, the conversion of cellulose to levulinates with H2SO4 gave at 200°C, respectively 50 and 14 % of esters in the primary and secondary alcohols. The use of sulfated zirconia and cesium phosphotungstate led to 15% of esters from primary alcohols, and 3% from secondary alcohol. The use of olefins as alcohol substituents was studied in the presence of sulfuric acid. With n-butene, the esterification of levulinic acid gave 55% of sec-butyl levulinate at 100°C and in the absence of solvent. From cellulose, 19% yield was obtained at 100°C in iso-octane. With iso-butene, 50% of tert-butyl levulinate was obtained from levulinic acid, without solvent and at 25°C. In the presence of Amberlyst-15, 80% yield was obtained, with a reuse up to 6 times of the catalyst without significant deactivation
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20

Walker, Gail Robertson. "Alkylation of 1-butene with isobutane using EMT and Y zeolites." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0023/NQ51236.pdf.

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21

Stewart, Iain Hunter. "Supercritical alkylation of isobutane with 1-butene using solid acid catalysts." Thesis, University of Liverpool, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367029.

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22

Stewart, Iain Hunter. "Supercritical alkylation of isobutane with 1-butene using solic acid catalysts." Thesis, University of Liverpool, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367174.

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23

Aldossary, Mohammed. "The alkylation of 2-butene with isobutane over large-pore zeolites." Thesis, University of Manchester, 2018. https://www.research.manchester.ac.uk/portal/en/theses/the-alkylation-of-2butene-with-isobutane-over-largepore-zeolites(bc8b7db9-82e5-4651-88a7-53facfafbc0f).html.

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The growing demand for higher quality gasoline coupled with stringent environmental regulations necessitates the reduction in aromatics, sulfur and nitrogen compounds. The alkylation process utilises low value olefinic gases produced in the refinery with isobutane to produce high octane gasoline that is free from aromatics, sulfur, and nitrogen compounds. Current alkylation technologies utilise hydrofluoric or sulfuric acids as catalysts for the reaction. Both acids however present health and environmental concerns along with high operational and mitigation costs. Zeolites are an ideal alternative to both acids due to their benign nature and acidic properties. Catalyst deactivation remains a major challenge for a zeolite-based alkylation process. Using a well-mixed reactor under ideal reaction conditions and relatively high flow rates, the alkylation of 2-butene with isobutane was studied over large pore zeolites. The effect of zeolite structure, of manipulating the acidity of the zeolite and of diluting the zeolite with additives on activity, stability and alkylate selectivity were examined. Examining the effect of the zeolite structure indicated that a three-dimensional channel system was required for the reaction. Zeolites Beta and Y exhibited higher stability and selectivity while MOR deactivated rapidly. The rapid deactivation in MOR was attributed to the lack of intersecting side-channels which prevented the bulky molecules from escaping the pores thus causing faster pore blockages. Varying the Si/Al ratio for zeolite Beta (12.5, 75, and 150) indicated that high aluminium content was required for the reaction. The siliceous Beta zeolites deactivated rapidly and mainly produced oligomerisation products. Lanthanum impregnation on the lowest Si/Al Beta zeolite reduced the Bronsted acidity and the impregnation procedure created Lewis acidity, both effects combined to reduce the activity and selectivity of the zeolite. The Si/Al ratio was varied for zeolite Y ranging from 2.6 to 30. The optimum ratio was the lowest, 2.6. Increasing the Si/Al ratio decreased the acidic sites available for the reaction and reduced the alkylate selectivity. Lanthanum exchange was shown to significantly improve the catalytic stability due to the reduction in the strong Lewis acidity. The optimum number of exchanges was three followed by calcination. This procedure created the highest ratio of strong Bronsted/strong Lewis acidity and enhanced the stability of the catalyst. Diluting the Y zeolite provided the most significant improvement on the catalytic stability. Silica additives, and particularly MCM-41, were shown to reduce the oligomerisation and enhance the alkylate production. The improvement was attributed to the separation of the zeolite clusters which reduced the olefin concentration and promoted alkylation. The optimum additive, MCM-41, had the highest surface area. Increasing the additive content did not provide additional improvements as the initial dilution seemed the most significant. Finally, the optimum catalysts from each section were compared for their stability and alkylate selectivity.
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24

YOO, KYESANG. "Development of Clean Catalyst for Alkylation of Isobutane with 2-Butene." University of Cincinnati / OhioLINK, 2003. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1060899661.

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25

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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26

Hobbs, Paul Michael. "Computational sorption studies of alkanes and alkenes in zeolites." Thesis, University of Reading, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.320085.

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27

Feller, Andreas. "Reaction mechanism and deactivation pathways in zeolite catalyzed isobutane-2-butene alkylation." [S.l. : s.n.], 2003. http://deposit.ddb.de/cgi-bin/dokserv?idn=967127483.

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28

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.<br>MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE.<br>Bibliography: leaves 274-283.<br>by Mark Richard Stening Manton.<br>Ph.D.
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29

Wanjale, S. D. "Crystallization, phase transformation and thermo-mechanical studies of poly(1-butene) nanocomposites." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 2007. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/2588.

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30

Beníček, Lubomír. "The interrelations between supermolecular structure, properties and degradability of isotactic poly(1-butene)." Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2009. http://tel.archives-ouvertes.fr/tel-00725695.

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Cette thèse porte sur l'inter relation entre la superstructure moléculaire, les propriétés et la dégradabilité du poly butène isotactique. L'évolution la plus importante est une transformation de phase particulière de la forme cristalline II à la forme cristalline I après cristallisation du polymère à partir de l'état fondu. Cette transformation a été caractérisée par calorimétrie, par diffraction des rayons X aux grands angles et par l'analyse des propriétés mécaniques en fonction des conditions de thermique de recuit. L'effet de la mise en forme sur la superstructure résultante a été mis en évidence sur des échantillons obtenus par injection ou par extrusion en utilisation les propriétés mécaniques en traction. Du fait de la très grande sensibilité du PB-1 vis-à-vis de la photodégradation des effets significatifs sur les propriétés thermiques et sur la transformation de phase ont été observés. Une caractérisation multi-échelle en photodégradation a été réalisée à partir d'analyses calorimétriques, d'analyse en spectroscopie infrarouge, de la diffraction des rayons X et des propriétés mécaniques en traction et ceci tant en photovieillissement en conditions accélérées qu'en conditions d'exposition naturelle.
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31

Benicek, Lubomir. "The interrelations between supermolecular structure, properties and degradability of isotactic poly(1-butene)." Clermont-Ferrand 2, 2009. http://www.theses.fr/2009CLF21921.

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Cette thèse porte sur l'inter-relation entre la superstructure moléculaire, les propriétés et la dégradabilité du poly butène isotactique. L'évolution la plus importante est une transformation de phase particulière de la forme cristalline II à la forme cristalline I après cristallisation du polymère à partir de l'état fondu. Cette transformation a été caractérisée par calorimétrie, par diffraction des rayons X aux grands angles et par l'analyse des propriétés mécaniques en fonction des conditions de thermique de recuit. L'effet de la mise en forme sur la superstructure résultante a été mis en évidence sur des échantillons obtenus par injection ou par extrusion en utilisation les propriétés mécaniques en traction. Du fait de la très grande sensibilité du PB-1 vis-à-vis de la photodégradation des effets significatifs sur les propriétés thermiques et sur la transformation de phase ont été observés. Une caracterisation multi-échelle en photodégradation a été réalisée à partir d'analyses calorimétriques, d'analyse en spectroscopie infrarouge, de la diffraction des rayons X et des propriétés mécaniques en traction et ceci tant en photovieillissement en conditions accélérées qu'en conditions d'exposition naturelle
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32

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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33

Loh, Andrea. "Study of the adsorption and reaction of 1-epoxy-3-butene on platinum(111)." Connect to online resource, 2007. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:1447652.

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34

Owino, Norbert Oduor. "Development of synthetic methods for the preparation of cyclobutenes and glycopeptides." Diss., Online access via UMI:, 2004. http://wwwlib.umi.com/dissertations/fullcit/3150497.

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35

McClean, Deaghlan Martin. "A kinetic study of the oligomerization of propene, butene and various hexenes over solid phosphoric acid." Thesis, University of Cape Town, 1987. http://hdl.handle.net/11427/23295.

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36

JAMMUL, NORALDEEN. "Etude physico-chimique des catalyseurs v#2o#5-tio#2. Cinetique d'oxydation du butene-1." Paris 6, 1989. http://www.theses.fr/1989PA066607.

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L'oxydation du butene-1 en anhydride maleique a ete etudiee sur des catalyseurs v#2o#5-tio#2; ces derniers ont ete prepares par impregnation, co-precipitation d'ions ti#4#+ et v#5#+ ou v#4#+ (catalyseurs a et b). Les catalyseurs obtenus sont caracterises par les methodes suivantes: analyse x, rayons x, rpe, spx, ir. L'analyse par rayons x a montre l'existence d'une solution solide tio#5(vo#2)#x. L'analyse par spx nous a permis de conclure que les modeles des tours de v#2o#5 sur l'interface tio#2(vo#2)#x ou sur surface nue de tio#2 sont plus proches du comportement de nos catalyseurs que celui de bond (tours de v#2o#5 sur monocouche vo#x). L'etude cinetique montre l'existence de correlations entre les selectivites des produits et le taux de recouvrement de tio#2 par v#2o#5 cristallise. Parmi les catalyseurs etudies, le catalyseur a a conduit aux meilleures performances catalytiques
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37

Al-Aeeb, Ahmed. "The synthesis of 1-butene oligomers with vinyl endgroups and their use in further reactions." Thesis, Link to the online version, 2007. http://hdl.handle.net/10019/379.

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38

Mazoyer, Etienne. "Nouvelle génération de catalyseurs a base de tungstène supporté sur oxydes pour la production du propylène." Thesis, Lyon 1, 2010. http://www.theses.fr/2010LYO10169/document.

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La préparation de nouveaux catalyseurs à base de tungstène par la voie Chimie Organométallique de Surface a été abordée dans cette thèse pour la production du propylène à partir de l'éthylène et/ou de butènes. Deux types de systèmes catalytiques ont été développés. Des hydrures de tungstène supportés, obtenus par réaction de surface entre un complexe de tungstène [W(CtBu)(CH2 tBu)3] et la -alumine suivi d'un traitement sous H2 à 150°C ont été préparés. Les caractérisations par différentes techniques spectroscopiques (IR, RMN solide, Raman et EXAFS) et réactivité stoechiométrique ainsi que les modélisations par calculs théoriques (DFT) ont montré la présence à la surface de deux espèces trishydrures : neutre et cationique. Ce catalyseur s'est révélé particulièrement actif pour la conversion directe de l'éthylène en propylène à 150°C selon un mécanisme trifonctionnel (dimérisation, isomérisation et métathèse croisée). L'accent a été mis sur la détermination du mode de désactivation par oligomérisation de l'éthylène, due principalement à la présence en surface d'espèce cationique. Pour pallier ce problème, d'autres réactions permettant la production de propylène avec de meilleures activités ont été développées (conversion des butènes, métathèse croisée éthylène/2-butène, 2-butène/isobutène). La conversion directe de 2-butène en propylène, inconnue jusqu'à lors, a notamment été étudiée. Enfin, un second type de systèmes catalytiques, modèles du site actif de l'hydrure de tungstène supporté et du catalyseur industriel WO3/SiO2, a été préparé et caractérisé. Ces nouveaux catalyseurs, portant un ligand oxo, se sont montrés bien plus actif en métathèse des oléfines que leurs homologues portant un ligand imido. Ces derniers se désactivent rapidement par décomposition de métallacyclobutane entraînant une réduction du tungstène non observée dans le cas des systèmes oxo<br>The preparation of new tungsten based catalyst using Surface Organometallic Chemistry is described in this thesis. These catalysts have been prepared for the production of propylene from ethylene and/or butenes. Two types of catalyst have been developed. Supported tungsten hydrides, resulting from the surface reaction of [W(CtBu)(CH2 tBu)3] with -alumina followed by a treatment under H2 at 150°C have been prepared. The characterizations by several spectroscopic techniques (IR, SSNMR, Raman and EXAFS) and stoichiometric reactivity combined by with theoretical calculations (DFT) have demonstrated the presence of two tungsten hydride surface species: a neutral and a cationic. This catalyst have shown outstanding reactivity for the direct conversion of ethylene to propylene 150°C following a tri-functional mechanism (dimerization, isomerization and crossmetathesis). The deactivation pathway has been attributes to ethylene oligomerization mainly due to the presence of cationic surface species. To circumvent this deactivation, other reactions affording propylene have been developed (butenes conversion, ethylene/2-butene and isobutene/2-butene cross metathesis). The conversion of 2-butene to propylene, until then unreported, has been notably studied. Finally, a second type of catalyst, models of the active site of supported tungsten hydrides and of WO3/SiO2 catalyst, has been prepared and characterized. These new catalysts, bearing an oxide ligand, have been shown to be more active than their imido counterparts. These later deactivates quikely by metallacyclobutane decomposition leading to the reduction of the tungsten non observed in the case of oxo systems
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39

Aouali, Leïla. "Etude de catalyseurs palladium-zeolithe stabilisee : influence des conditions de preparation sur la formation et la reactivite des particules metalliques obtenues." Paris 6, 1987. http://www.theses.fr/1987PA066243.

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40

Burckle, Eric C. "COMPARISON OF ONE-, TWO-, AND THREE-DIMENSIONAL ZEOLITES FOR THE ALKYLATION OF ISOBUTANE WITH 2-BUTENE." University of Cincinnati / OhioLINK, 2000. http://rave.ohiolink.edu/etdc/view?acc_num=ucin971274379.

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41

Birsoy, Öniz Yılmaz Selahattin. "Effects of metal cation on the skeletal isomerization of n-Butene over ZSM-5 and ferrierite/." [s.l.]: [s.n.], 2005. http://library.iyte.edu.tr/tezler/master/kimyamuh/T000432.pdf.

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42

Zheng, Quanxing. "Conversion of 2,3-butanediol over bifunctional catalysts." Diss., Kansas State University, 2016. http://hdl.handle.net/2097/34461.

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Doctor of Philosophy<br>Department of Chemical Engineering<br>Keith L. Hohn<br>In this study, Cu/ZSM-5 catalysts were used to catalyze the hydrodeoxygenation of 2,3-butanediol to butenes in a single reactor in the presence of hydrogen. The carbon selectivity of butenes increased with increasing SiO₂/Al₂O₃ ratio (lowering acidity of zeolite) and H₂/2,3-butanediol ratio. Cu/ZSM-5 with a SiO₂/Al₂O₃ ratio of 280 showed the best activity toward the production of butenes. On zeolite ZSM-5(280), the carbon selectivity of butenes increased with increasing copper loading and 19.2wt% of CuO showed the highest selectivity of butenes (maximum 71%). The optimal reaction temperature is around 250 °C. Experiments demonstrated that methyl ethyl ketone (MEK) and 2-methylpropanal are the intermediates in the conversion of 2,3-butanediol to butenes. The optimal performance toward the production of butene is the result of a balance between copper and acid catalytic functions. Due to the functionalized nature of 2,3-butanediol, a variety of reactions can occur during the conversion of 2,3-butanediol, especially when multiple catalyst functionalities are present. To investigate the role of the metal (Cu) and acid sites in the process of reaction, the reaction kinetics for all major intermediate products (acetoin, MEK, 2-methylpropanal, 2-butanol and 2-methyl-1-propanol) were measured over Cu/ZSM-5(280), HZSM-5(280), and Cu/SiO₂ at 250 °C. The results showed that Cu is the active site for hydrogenation reactions, while the acidic sites on the zeolite are active for dehydration reactions. In addition, dehydration of alcohols over the zeolite is much faster than hydrogenation of ketone (MEK) and aldehyde (2-methylpropanal). A kinetic model employing Langmuir-Hinshelwood kinetics was constructed in order to predict 2,3-butanediol chemistry over Cu/ZSM-5(280). The goal of this model was to predict the trends for all species involved in the reactions. Reactions were assumed to occur on two sites (acid and metal sites) with competitive adsorption between all species on those sites. Two different types of mesoporous materials (Al-MCM-48, Al-SBA-15) and hierarchical zeolite (meso-ZSM-5) were loaded with ~20wt% CuO and investigated in the conversion of 2,3-butanediol to butenes. The results showed that the existence of mesopores on the catalysts (Al-MCM-48 and Al-SBA-15 types) could decrease the selectivities of products from cracking reactions, especially C₃= and C₅=−C₇= by comparison with the catalyst with ~20wt% CuO loaded on the regular HZSM-5(280); meanwhile, the selectivity of C₈= from oligomerization of butenes was found to increase with increasing pore size of the catalysts. With respect to Cu/meso-ZSM-5(280) catalyst, it can be seen that the catalyst performs in a similar way to both Cu/ZSM-5(280) catalyst and mesoporous copper catalysts (Cu/Al-MCM-48 and Cu/Al-SBA-15) since both micropores (diameter of ~0.55 nm) and mesopores (pore size of ~23 nm) exist on meso-ZSM-5(280). The results from Cu catalysts were compared with four other metal catalysts (Ni, Pd, Rh and Pt). It was found that Cu is not very active for hydrogenation of butenes, but is active for hydrogenation of carbonyl groups (C=O) to form hydroxyl groups (−OH). Pd, on the other hand, is active in further hydrogenating butenes and other unsaturated hydrocarbons. Both Ni and Rh catalysts are good for hydrogenation of olefins and cracking of heavy hydrocarbons; however, Rh is not as good as Ni for the hydrogenation of the carbonyl group (C=O) of MEK. In addition, Pt favors the formation of heavy aromatics such as 5-ethyl-1,2,3,4-tetrahydro-naphthalene, while Pd is active for the production of xylene.
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43

Bhowmik, Swati. "Development of analytical methods for the gas chromatographic determination of 1,2-epoxy-3-butene, 1,2:3,4-diepoxybutane, 3-butene-1,2-diol, 3,4-epoxybutane-1,2-diol and crotonaldehyde from perfusate samples of 1,3-butadiene exposed isolated mouse and rat livers." [S.l. : s.n.], 2002. http://deposit.ddb.de/cgi-bin/dokserv?idn=967431743.

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44

Brittz, Geertruida. "Olefin skeletal isomerization of n-butene, n-hexene and n-octene using alumina-based catalysts / Geertruida (Trudie) Brittz." Thesis, North-West University, 2012. http://hdl.handle.net/10394/8729.

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Stringent standards to improve air quality and to protect human health are continuously implemented due to the environmental impact of auto emissions. As a result, researching options for alternative components or alternative processes are very important to continuously improve the octane number in the fuel pool. Therefore, by exploiting the high olefin (butene, hexene and octene) content part of the feedstocks, the overall aim of this study was to obtain olefin skeletal isomerization for the improvement of the RON in the refinery fuel pool. The influence of temperature variation (350 °C, 400 °C and 450 °C) on the performance of the different alumina catalysts (eta (η)-alumina, H-ZSM-5 and silicated alumina) was investigated. All experiments were performed using a fixed bed reactor at atmospheric pressure and a constant weight hourly space velocity of 5 h-1. The effect of the different conditions and additions on conversion and selectivity was determined. Eta alumina and the silicated alumina (Siralox 40) were proved to be the catalysts that were most prone to cause skeletal isomerization when in contact with longer carbon chains. Butene did not isomerize to a significant extent when contacted over either Eta alumina or Siralox 40. In the case of the zeolite catalyst (ZSM-5), none of the feeds isomerized and it was speculated that it could have been due to the high activity of ZSM-5 which made this catalyst more likely to cause side reactions rather than the preferred skeletal isomerization reaction.<br>Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2013
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45

Subramaniam, Chitra P. "Morphology, Crystallization and Melting Behaviors of Random Copolymers of Ethylene with 1-Butene, 1-Pentene and 1-Hexene." Diss., Virginia Tech, 1999. http://hdl.handle.net/10919/28064.

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The morphology, crystallization and melting behaviors of a series of ethylene/alpha-olefin copolymers were investigated as a function of comonomer content, comonomer type and processing conditions, including crystallization temperature and time. This was achieved by using a combination of techniques such as Nuclear Magnetic Resonance Spectroscopy (NMR), Differential Scanning Calorimetry (DSC), Atomic Force Microscopy (AFM) and Fourier Transform Infrared Spectroscopy (FTIR). The results from the thermal analysis studies clearly indicated the existence of two distinct regions of crystallization, demarcated by a cross-over temperature, 𝑇*. The high temperature region (above 𝑇*) displayed cooling-rate dependence as well as significant hysteresis in crystallinity between cooling and heating processes, similar to that observed in linear polyethylene. This implied that the crystals associated with this region were formed via chain-folded lamellar growth. However, the lower temperature region (below 𝑇*) exhibited reversible changes in crystallinity between cooling and heating, and was found to be independent of the cooling rate. The temporal evolution of secondary crystallization in the copolymers was studied for times ranging from 100-106 min, at different crystallization temperatures (Tx). Two distinct melting endotherms were discerned at crystallization temperatures below 𝑇*. A higher melting endotherm that remained invariant with crystallization time (tx) was associated with lamellar crystals that were formed during primary crystallization. In contrast, both the positions as well as the magnitude of the lower temperature endotherm were found to vary systematically with log (tx). The peak positions of the low endotherm, i.e., the melting temperature of the secondary crystals, were found to consistently extrapolate to the crystallization temperature at very short times. Based on this and other considerations, the secondary crystals were associated with the melting of thin stacks of polymer chains aggregated in the form of "fringed-micelle"-like bundled crystals. The temperature dependence of the kinetic parameters (derived from Avrami and other analyses) above 𝑇* and their invariance below 𝑇*, suggested that the transformation in morphology from lamellar to bundled crystals was gradual and systematic, as the branch content was increased or as the crystallization temperature was lowered. Further verification of this result was obtained via AFM experiments. A systematic variation in morphology from lamellar to spot-like (lamellae were less clearly visible) was clearly discerned on increasing the comonomer content. Furthermore, a second morphological feature represented by bridge-like links between the lamellae, and approximately perpendicular to them, was also observed for some copolymers. This feature was correlated with the bundled crystals discussed above. The presence of an alternate crystal structure, in addition to the usual orthorhombic crystal form expected for linear polyethylene, was also established from the results of the FTIR studies. The relative proportions of the second crystal form in the copolymers as a function of branch content and temperature were modeled and estimated via mathematical deconvolution and curve-fitting processes. Comparing the results to those of the hexagonal rotator phase of n-paraffins, it was proposed that the second crystal structure in the copolymers could be assigned to a hexagonal type unit cell structure. Furthermore, the crystallization and melting behaviors of all three types of copolymers studied - ethylene/1-butene, ethylene/1-pentene and ethylene/1-hexene - were found to be identical to each other, suggesting that the crystallization process examined was independent of branch type for the ethyl, propyl and butyl branches examined. Since the lengthy butyl branch (in the ethylene-hexene copolymers) is not likely to be accommodated in the crystal, it was concluded that all three branch types were predominantly excluded from the crystal structure. Based on the results from these studies, a new model for the crystallization mechanism in these copolymers was proposed and could be further extended to other semicrystalline polymers such as PET, PEEK, PVC, PBT, i-PS and polycarbonate. In this model, the primary and secondary crystallization stages were redefined on the basis of the chain-folded lamellar growth process. According to the model, secondary crystallization involves the generation of the bundled crystals that may be viewed as physical cross-links in the amorphous phase. Therefore, it may provide a means of correlating the temporal evolution of secondary crystallization to the time and temperature dependence of the physical properties of semicrystalline polymers, above their glass transition temperatures.<br>Ph. D.
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Kumar, Amit. "Morphology, Crystallization and Melting Behavior of Statistical Copolymers of Propylene with Ethylene, 1-Butene, 1-Hexene and 1-Octene." Thesis, Virginia Tech, 2001. http://hdl.handle.net/10919/33563.

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In this thesis, the morphology, crystallization and melting behavior of polypropylene copolymers (propylene/ethylene, propylene/1-butene, propylene/1-hexene and propylene/1-octene) has been examined. The multiple melting behavior has been correlated with the presence of alpha and gamma phases and with the occurrence of cross-hatching morphology. The Crystallization and melting behavior of propylene/ethylene and propylne/1-butene are qualitatively similar and compatible with the expectations that the ethylene and butene comonomers are partly included in the propylene lattice. Propylene/1-hexene and propylene/1-octene copolymers exhibit remarkably similar behavior and morphologies consistent with the expectations that the hexene and the octene comonomers are rigorously excluded from the crystal lattice. The origin and the crystallization time dependence of the multiple melting behavior is very different for these two pairs of copolymers. For PE and PB it is consistent with the melting of parent a-phase lamellae and alpha or gamma-phase daughter lamellae. For PH and PO copolymers it is very similar to that observed for ethylene-octene(EO) and ethylene-styrene(ES) copolymers and compatible with the melting of primary lamellae and secondary mosaic or fringed micellar structures.<br>Master of Science
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47

Demirkan, Korhan Yılmaz Selahattin. "Influence of synthesis parameters on the properties of ZSM-5 & on their catalytic activity for 1-butene isomerization/." [s.l.]: [s.n.], 2002. http://library.iyte.edu.tr/tezler/master/kimyamuh/T000019.pdf.

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48

Hub, Serge. "Mécanismes d'hydrogénation des butène-1 et butyne-1 sur catalyseurs au palladium." Grenoble 2 : ANRT, 1986. http://catalogue.bnf.fr/ark:/12148/cb37598410d.

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Ehrmaier, Andreas [Verfasser], Johannes A. [Akademischer Betreuer] Lercher, Johannes A. [Gutachter] Lercher, and Klaus [Gutachter] Köhler. "Dimerization of 1-Butene on Ni Based Solid Catalysts / Andreas Ehrmaier ; Gutachter: Johannes A. Lercher, Klaus Köhler ; Betreuer: Johannes A. Lercher." München : Universitätsbibliothek der TU München, 2019. http://d-nb.info/1191897273/34.

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Ke, Yutian. "Elucidation of Chain-Folding Structure of Isotactic Poly(3-methyl-butene-1) in Bulk and Single Crystals by Solid-State NMR." University of Akron / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=akron1427824659.

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