Dissertations / Theses on the topic 'Formic acid synthesis'

Thesis (Ph. D.) -- University of Maryland, College Park, 2005.
Thesis research directed by: Chemical Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.

La síntesi de format i àcid fòrmic via la hidrogenació de diòxid de carboni ofereix un camí prometedor en la valorització de diòxid de carboni, i una alternativa atractiva als processos comercials actuals. No obstant, aquesta reacció no és termodinàmicament favorable en fase gas. Per això, l’ús d’additius bàsics juntament amb catalitzadors homogenis en processos per lots representa l’estat de l’art en aquest camp. L’escassa investigació d’aquesta reacció fent ús de catalitzadors heterogenis ha pogut dificultar el seu posterior desenvolupament a escala industrial. En aquest treball, es demostra la síntesi contínua de format a partir de CO2 i H2 utilitzant catalitzadors heterogenis i amb l’avantatge de treballar a alta pressió. D’una banda, en la presència de metanol, el producte de la reacció és metanoat de metil, que és un potencial intermedi en la síntesi contínua d’àcid fòrmic mitjançant la hidròlisi. S’aporten nous enfocs en relació amb la reactivitat dels metalls d’encunyació, els rols dels òxids metàl·lics com suports, i els intermediaris reactius, així com els mecanismes de reacció. D’altra banda, la incorporació d’aigua o trietilamina a la corrent d’alimentació sobre un catalitzador molecular heterogenitzats promou la formació d’àcid fòrmic. A més, s’explora el potencial d’utilitzar un material porós per a immobilitzar un complex molecular d’iridi. Aquesta tesi destaca la importància de fer ús de distintes metodologies conjuntament per a verificar la localització i naturalesa dels llocs actius del catalitzador, i facilita així el seu disseny racional.
La síntesis de formiato y ácido fórmico vía la hidrogenación de dióxido de carbono ofrece un camino prometedor en la valorización de dióxido de carbono, y una alternativa atractiva a los procesos comerciales. No obstante, esta reacción no es termodinámicamente favorable en fase gas. Por ello, el uso de aditivos básicos junto catalizadores homogéneos en procesos por lotes representa el estado del arte en este campo. La escasa investigación de esta reacción empleando catalizadores heterogéneos ha podido dificultar su posterior desarrollo a escala industrial. En este trabajo, se demuestra la síntesis continua de formiato a partir de CO2 e H2 utilizando catalizadores heterogéneos y con la ventaja de trabajar a alta presión. Por un lado, en la presencia de metanol, el producto de la reacción es metanoato de metilo, que es un potencial intermedio en la síntesis continua de ácido fórmico mediante la hidrólisis. Se aportan nuevos enfoques en relación con la reactivad de los metales de acuñación, los roles de los óxidos metálicos como soportes, y los intermediarios reactivos, así como los mecanismos de reacción. Por otro lado, la incorporación de agua o trietilamina en la corriente de alimentación sobre un catalizador molecular heterogeneizado promueve la formación de ácido fórmico. Además, se explora el potencial de utilizar un material poroso para inmovilizar un complejo molecular de iridio. Esta tesis destaca la importancia de emplear distintas metodologías conjuntamente para verificar la localización y naturaleza de los sitios activos del catalizador, facilitando así su diseño racional.
The synthesis of formates and formic acid by hydrogenation of carbon dioxide offers a promising path to valorise carbon dioxide and an appealing alternative to the commercial processes. However, such reaction is not thermodynamically favourable in gas phase. Thus, the use of basic additives together with homogeneous catalysts under batch conditions represent the state-of-the-art in this field. The scarce research on this reaction over heterogeneous catalysts may have hindered its further development at industrial scale. In this work, the continuous synthesis of formates from CO2 and H2 is demonstrated over heterogeneous catalysts, while taking advantage of high-pressure conditions. On one hand, in the presence of methanol, the reaction product is methyl formate, which can be a potential intermediate in the continuous synthesis of formic acid through its hydrolysis. New insights are provided regarding the reactivity of coinage metals, the roles of metal oxides as supports, and the reactive intermediates and reaction mechanisms. On the other hand, the cofeeding of water or triethylamine over a heterogenized molecular catalyst promotes the formation of formic acid. The potential of using a covalent triazine framework to immobilize an iridium molecular complex, as well as of the unique properties of the resulting material in CO2 hydrogenation reactions is explored. This thesis highlights the importance of employing combined methodologies to verify the location and nature of active sites, which can facilitate rational catalyst design by tuning active metal and support materials.

Carbon nanostructures are a wide field with many applications. The use of carbon nanostructures as support in heterogeneous catalysis is a key development that led together with the use of nanoparticles to a significant cost reduction of catalysts. Catalysts designed in this way are widely applied in fuel cell technologies. For portable devices especially low temperature fuel cells are desirable with low hazards for the user. One technology which fulfills these requirements is the direct formic acid fuel cell (DFAFC). DFAFC have many promising characteristics, such as high electromotive force and easy fuel handling. However, they still suffer from too low power output and lifetime for commercialization. This thesis focusses on two main aspects: the synthesis of carbon nanostructures by chemical vapor deposition (CVD) and their application as catalyst support. The materials are investigated by many different techniques ranging from transmission electron microscopy (TEM) to fuel cell tests. Different carbon nanostructures could be synthesized by catalytic CVD on palladium (Pd) nanoparticles. Multi-walled carbon nanotubes (MWCNTs), carbon nanofibers (CNFs) and helical carbon nanofibers (HCNFs) were grown, selectively, dependent on temperature, using acetylene as carbon precursor. Especially HCNF raised further interest due to their unique structure. A growth model for HCNFs was developed based on an anisotropic extrusion model. The synthesis conditions for HCNFs were optimized until an almost 100 % purity with very high efficiency was obtained. The unique helical but fiber-like structure made the material very interesting as support for heterogeneous catalysis. Several catalysts based on Pd nanoparticle decorated HCNFs were developed. The synthesis methods ranged from standard methods like the polyol method to phase-transfer methods. The catalysts showed very promising results for the electro-oxidation of methanol, ethanol and formic acid. This makes them highly attractive for fuel cell applications. The catalysts were tested in DFAFC. The superiority of HCNF-based catalysts is attributed to the good attachment of nanoparticles to the defect-rich and easy to functionalize surface of HCNFs in combination with adequate film forming properties during electrode preparation.
Nanostrukturerat kol är ett mycket brett fält med ett stort antal tillämpningar. Användning av kolnanostrukturer som support för heterogena katalysmaterial har tillsammans med utvecklingen av nanopartiklar lett till en avsevärd minskning av kostnaden för katalysatorer. Katalysatorer designade på detta sätt används frekvent i bränsleceller. För portabla tillämpningar är utvecklingen av säkra och miljövänliga lågtemperaturceller mycket viktig. En teknologi som uppfyller dessa kriterier är bränsleceller som drivs med myrsyra (DFAFC). Sådana bränsleceller har många önskvärda egenskaper, såsom en hög elektromotorisk kraft och en enkel hantering av bränslet. Trots dessa goda egenskaper har de också en del nackdelar som hindrar en full kommersialisering. De två mest problematiska är en för låg genererad effekt samt en för kort livslängd på katalysatorerna. Denna avhandling fokuserar på två huvudpunkter som adresserar dessa problem; tillverkning och karaktärisering av kolnanostrukturer producerade med CVD, och deras tillämpningar som support för katalysatorer. Materialen karaktäriseras med en rad olika tekniker, allt från transmission-elektronmikroskopi till bränslecellstester. Olika kolnanostrukturer har syntetiserats med katalytisk CVD på palladium (Pd) nanopartiklar. Produktionen av flerväggiga kolnanorör, kolfibrer och heliska kolnanofibrer har tillverkats med acetylen som kolkälla och genom att variera temperaturen kunde innehållet av olika typer av nanostrukturerat kol kontrolleras. Särskilt stort intresse har de heliska kolnanofibrerna rönt på grund av deras unika struktur. Vi beskriver en tillväxtmekanism baserad på en anisotrop diffusionsmodell. Genom att justera produktionsparametrarna visar vi att heliska kolnanofibrer kunde tillverkas med nära 100 %-ig renhet och hög effektivitet. Den unika heliska och fiberlika strukturen är mycket intressant for tillämpningar som support för heterogena katalysatorer. Ett flertal kompositer för katalytiska tillämpningar har utvecklats baserade på heliska kolnanofibrer, dekorerade med heterogena katalysatorer genom en rad olika kemiska/fysikaliska tekniker. De syntetiserade materialen visar mycket goda katalytiska egenskaper för att oxidera metanol, etanol och myrsyra. Därigenom blir de mycket attraktiva för användning i bränsleceller. Vi korrelerar de goda katalytiska egenskaperna med en bra vidhäftning av nanopartiklarna på de heliska kolnanofibrerna defekter, deras goda ledningsförmåga, bra egenskaper för att förbereda elektroder, samt deras stora yta i förhållande till deras volym och vikt.

Surface catalysed reactions play an important role in chemical productions. Developments of catalyst requiring high activity whilst improving on product selectivity can potentially have a profound effect in the chemical industry. Traditional catalyst modifications were focused on tuning the size, shape and foreign metal doping to form well defined metal nanoparticles of unique functionalities. Here, we show new approach to engineering of metal nanocatalysts via a subsurface approach can modify the chemisorption strength of adsorbates on the surface. Carbon modified nanoparticles were synthesised using glucose to stabilise Pd nanoparticles at a molecular level. Upon heat treatment, the carbonised glucose encapsulated the Pd nanoparticles with carbon atoms take residence in the octahedral holes (15 at.%). These materials were tested in liquid phase stereoselective hydrogenations of 3-hexyn-1-ol and 4-octyne. The former has importance in the fragrance industry towards the production of leaf fragrance alcohol. It was shown for the first time that the geometrically and electronically modified Pd with interstitial carbon atoms reduced the adsorption energy of alkenes, ultimately leading to higher reaction selectivity. Boron modified Pd nanoparticles was synthesised using BH₃.THF in the liquid phase. The material possess high B interstitial saturation (20 at.%), which can be synthesised for the first time below 100°C. These materials were tested in the liquid phase selective hydrogenation of various alkynes and 2-chloronitrobenzene, of which the latter has importance in the pesticides industry. Kinetic modelling on the hydrogenation of 4-octyne suggests these subsurface occupied B does play a pivotal role on increasing the reaction selectivity, as removal of these species lead to decreased selectivity. Au nanoparticles were synthesised and characterised using H¹³COOH NMR. The new liquid NMR characterisation method is successfully applied to examine the chemisorption strength of metal nanoparticles. An attempt to synthesise PVP capped B modified Pd nanoparticles with the above NMR characterisation was investigated. It is believed the examples of subsurface atom modifications as shown here may offer future catalyst developments in this area.

Doctor of Philosophy (PhD)
This thesis describes synthetic studies towards the HIV-1 integrase inhibitory natural products lithospermic acid and integramycin, resulting in a formal total synthesis of the former. A modular, flexible and convergent synthetic strategy to lithospermic acid was devised. In this approach, a Sonogashira coupling was used to unite the C1–C7 and C20–C27 fragments that were subsequently manipulated to then participate in the key step of the synthesis, a palladium-mediated carbonylative annulation. Reduction of the benzofuran nucleus with magnesium in methanol then provided the desired dihydrobenzofuran core of lithospermic acid. Various protecting group strategies were investigated to complete this sequence in an efficient manner. Further synthetic manipulations afforded the complete C1–C9/C19–C27 fragment, which was united with the C10–C18 fragment to deliver the entire carbon skeleton of lithospermic acid. A two step deprotection sequence was undertaken, however, complications with the final deprotective step prevented definitive proof that the total synthesis of lithospermic acid had been achieved. An alternate protecting group strategy was sought, and a formal total synthesis of lithospermic acid was achieved by intercepting an advanced intermediate from a previous total synthesis. Several strategies for the enantioselective synthesis of the dihydrobenzofuran core of lithospermic acid were evaluated, however, none proved successful. A synthetic route towards the tetramic acid subunit of integramycin was also investigated. 3- Methoxymaleimide was constructed using known chemistry, and the regioselective reduction of this ring system was developed. Attempts to further functionalise this ring system were thwarted by difficulties associated with handling. The scope of the regioselective reduction was investigated on an array of N- substituted methoxymaleimides with the procedure found to be generally high yielding and highly regioselective.

Dans la synthèse des matériaux catalytiques, deux aspects orientent en particulier les recherches actuelles: le contrôle de taille afin d'obtenir des nanoparticules finement divisées et le contrôle précis de la morphologie. Dans cette étude, nous avons utilisé les milieux non aqueux pour élaborer des matériaux catalytiques à base d'oxydes des métaux de transition (Ti, Zr, Mn). Trois méthodologies ont été employées pour la préparation des solides à base de TiO2. La synthèse dans les nitrates fondus dopés avec différents anions permet un boncontrôle des propriétés texturales des matériaux et de la nature des plans cristallins exposés. Les préparations utilisant le nitrate d'ammonium stabilisé avec des molécules organiques azotées conduit à des solides présentant des tailles et des formes de particules variables en fonction de la nature du stabilisateur. Le traitement à reflux dans des solvants organiques polaires conduit à l'obtention des supports TiO2 de grandes surfaces spécifiques. Pour la valorisation catalytique de ces matériaux, deux réactions appliquées au domaine de la photocatalyse ont été employées: la production d'H2 par déshydrogénation du méthanol etl'oxydation photocatalytique de l'acide formique. La réaction modèle de décomposition del'isopropanol a été utilisée comme test de caractérisation des propriétés acido-basiques de nossystèmes. La technique de nitrates fondus a été également appliqué avec succès pourl'obtention en une seule étape des catalyseurs supportés Mn-Zr et Mn-Ti. Ces catalyseursmontrent une excellente activité pour l'oxydation totale de composés organiques volatils(COV).

Abstract Climate change and global warming are currently widely discussed topics, both of which potentially impact all the nations and industries. Carbon dioxide (CO2) and other green house gases (GHG) are seen as a major challenge. This doctoral dissertation aims to conduct techno-economic calculations on the possibilities of reducing the industrial use of fossil raw materials in Northern Finland. This doctoral dissertation analyses industrial CO2 emissions from five complementary perspectives: identifying significant potential industrial plants, analysing the replacement of fossil raw materials with wood biomass, considering combining different industrial sectors, the potential of biogas as industrial raw material, and estimating the economic significance of moisture in wood fuel. The study started by analysing all the relevant 262 regional environmental permits to find the significant industrial users of synthesis gas in the studied region. Processes used by each identified case were analysed carefully to identify the most potential change possibilities. Economic calculations were conducted for these cases using true production volumes. The aim was to reach solutions that were economically sound. Five industrial sites were identified as potential cases for replacing raw materials of synthesis gas or hydrogen with renewable alternatives. These sites include the Rautaruukki steel mill, Eka Chemicals’ hydrochloric acid plant, Kemira’s formic acid plant, Kemira’s hydrogen peroxide producing plant, and Talvivaara mining’s hydrogen plant. The main implications of this dissertation include providing tips for industrial managers, regional decision makers and legislators. Managers of companies with high energy consumption and/or high usage of fossil raw materials in their products can benefit from the results of this dissertation the most. Managers should conduct similar calculations, as in this study, by using exact figures relevant to their processes and raw materials. This doctoral dissertation also suggests finding new solutions for replacing fossil raw materials by combining two different industrial sectors, e.g. steel and chemical industries. Regional decision makers may utilise the calculations presented in this doctoral dissertation when developing regional strategies
Tiivistelmä Ilmaston muutos ja globaali lämpeneminen ovat tällä hetkellä laajasti keskusteltuja aiheita, ja ne vaikuttavat kaikkiin maihin ja kaikkiin teollisuuden aloihin. Hiilidioksidi (CO2) ja muut kasvihuonekaasut nähdään suurena haasteena. Tämä väitöskirja pyrkii teknistaloudellisten laskelmien avulla tutkimaan mahdollisuuksia vähentää fossiilisten raaka-aineiden käyttöä Pohjois-Suomen alueella. Tämä väitöskirja analysoi teollisia CO2-päästöjä viidestä toisiaan täydentävästä näkökulmasta: identifioimalla merkittäviä teollisia tuotantolaitoksia, analysoimalla fossiilisten raaka-aineiden korvaamista puubiomassalla, tutkimalla erilaisten teollisten tuotantolaitosten yhdistämistä, tutkimalla biokaasun käyttöä mahdollisena teollisuuden raaka-aineena ja arvioimalla kosteuden taloudellista merkitystä puupolttoaineessa. Tutkimus alkoi analysoimalla kaikki alueen identifioidut 262 ympäristölupaa, jotta merkittävät synteesikaasun käyttäjät tulisivat esille. Jokaisen löydetyn tapauksen tuotantoprosessit analysoitiin huolellisesti, jotta potentiaalisimmat muutosmahdollisuudet huomioitaisiin. Teknistaloudellisia laskelmia tehtiin näille tapauksille käyttämällä todellisia tuotantolukuja. Tarkoituksena oli löytää taloudellisesti kannattavia vaihtoehtoja. Viisi teollista tuotantolaitosta identifioitiin tapauksiksi, joissa synteesikaasun tai vedyn raaka-aine voitaisiin korvata uusiutuvilla raaka-ainevaihtoehdoilla. Nämä tuotantolaitokset olivat Rautaruukin terästehdas, Eka Chemicalsin kloorivetyhapon tuotantolaitos, Kemiran muurahaishappotehdas, Kemiran vetyperoksiditehdas ja Talvivaaran kaivoksen vedyn tuotantolaitos. Tärkeimmät implikaatiot tästä väitöskirjatyöstä sisältävät pohdittavia ajatuksia teollisille toimijoille, alueellisille päätösten tekijöille ja lainsäätäjille. Korkean energian kulutuksen ja/tai suurten fossiilisten raaka-ainekäyttöjen yhtiöissä päätöksentekijät voivat hyödyntää parhaiten tämän väitöskirjan tuloksia. Päätöksentekijät voisivat käyttää esimerkkeinä tämän väitöskirjan laskelmia tehdessään omia analyyseja, jolloin heidän tulisi käyttää tarkkoja lukuja yritystensä prosesseista ja raaka-ainekäytöistä. Tämä väitöskirja ehdottaa myös etsimään uusia ratkaisuja fossiilisten raaka-aineiden korvaamisessa yhdistämällä tuotannollisesti erilaisia teollisia sektoreita esimerkiksi teräksen ja kemian tuotteiden valmistuksen. Alueelliset päätösten tekijät voivat hyödyntää väitöskirjassa esitettyjä laskelmia alueellisten strategioiden kehitystyössä

Chiral alpha-branched amines are common substructures of bioactive synthetic targets such as alkaloids and amino acids. Direct asymmetric amine synthesis by addition to the C=N bond of carbonyl imino derivatives is promising and efficient to introduce the stereogenic center and carbon-carbon bond in one step. Furthermore, disconnection of either C-C bond at the amine stereogenic center would be the most versatile method to achieve this objective; we could make the choice depending on the different synthetic strategies, such as the availability of precursors and the presence of complicating structural features. In our group, we disclosed that manganese carbonyl mediates stereoselective photolytic radical addition of alkyl iodides to chiral imino acceptors, which is a powerful tool to form a new C-C bond and generate a chiral center. Qualitative mechanistic studies confirm the importance of free radicals, imply that this is a nonchain (or short chain length) free-radical process, and reveal that organomanganese compounds are not a viable source of alkyl radical for the addition reactions under the conditions in our lab. In my thesis, we have extended the application of our methodology. At the beginning of my research, our Mn-mediated addition methodology was first applied to accomplish the couplings of iodides and ketone N-acylhydrazones, generating quaternary carbon stereocenters and offering access to a variety of alpha-alkylated alanine analogs. These radical additions complement enolate alkylation methodologies, as they occur under nonbasic conditions and permit introduction of both primary and secondary alkyl groups with relative ease. The versatility with respect to the iodide is a distinguishing feature of the Mn-mediated coupling that foreshadows application to more complex targets. Secondly, a Mn-mediated radical-ionic annulation strategy was validated as a synthetic route to quinine. Intermolecular radical addition to C=N bonds has rarely been applied as a strategic bond construction in natural product synthesis; this synthesis of quinine offers the strongest demonstration yet of the utility of such reactions in application toward complex multifunctional targets.

In this thesis, it has been studied the deamination of aromatic amines, through in situ formed diazonium salts as reaction intermediates, catalyzed by salicylic acid, a nontoxic, eco-friendly and economic catalyst. In the early part of the thesis (Chapter I) it has studied the deamination process using THF as solvent as hydrogen donor and anilines as radical source, to carry the hydrodeamination reaction, as well as the process in its deuterodeamination manner using deuterated solvent. Following with this study in Chapter II and Chapter III, it has been studied the addition of the aromatic radicals, generated with the methodology employed in the first chapter, to different types of double bond, to form α-arylketones (Chapter II) and γ-aryl lactones, throw a following intramolecular cyclization (Chapter III). Finally, in Chapter IV was studied the construction of arylphosphonates, starting from anilines as radical source, and triphenylphosphite, and in this case specially, mechanism was hard explored. In every work, the methodologies could be scaled-up above 1 g, reaction mechanisms were proposed and studied through control and mechanistical experiments, and follow reactions were carried out.

Among heterocyclic compounds, quinoline scaffold has become an important motif for the development of new pharmacological active compounds. Since the discovery of their antimalarial properties, a large variety of quinolines was found to have interesting physiological activities and displayed attractive applications for pharmaceutical industries. In accordance to the above-mentioned features, a number of methods were developed for their synthesis but enantioselective versions are still lacking in the literature. In the past decades, this question has become even more complex, with the emergence of the less common axial chirality. Within the growing number of articles about atropisomers, the discovery of new synthetic pathways for the synthesis of enantioenriched atropisomers and their use in drug discovery has become a challenging topic in the organic chemistry scenario. In this work, the development of a novel atroposelective strategy for the synthesis of quinoline substrates has been achieved, and in order to obtain high values of enantioselectivity and yields a screening of the reaction conditions has been performed. The design of such strategy has been developed combining an already established methodology for the synthesis of heteroaromatic compounds such as a well-known Friedländer-type quinoline synthesis with chiral Brønsted acid catalysis to obtain the C-C bond formation in an enantioselective fashion.

Thesis (MScAgric)--University of Stellenbosch, 2003.
ENGLISH ABSTRACT: Coal mining in South Africa is estimated to produce 200 Ml of acid mine drainage (AMD) per day in the Pretoria-Witwatersrand-Vereeniging (PWV) area alone, while electricity production resulted in approximately 27 Mt of ash in 2001. A large number of collieries in South Africa are tied to power stations where these two waste streams, acid mine drainage and fly ash, have the capacity to neutralize each other and provide an opportunity for co-disposal. The aim of this study was to investigate the reactions that occur during the co-disposal of fly ash leachate (FAL) and AMD and to examine the precipitates that result from the neutralisation reactions. Potentiometric titration was employed to investigate the neutralisation of Al-Fe salt solutions, simulating acid mine drainage (AMD), with alkaline solutions of Ca or Na hydroxide as well as fresh alkaline leachate from fly ash (FAL). The effectiveness of fly ash in removing metals and other salts from acid mine water was examined by analysing the neutralised water and modelling the results thermodynamically. Precipitates, prepared from large scale synthetic AMD and FAL co-disposal at various pH levels and Fe:Al ratios, were characterised according to composition, mineralogy and surface properties. The experimental neutralisation of synthetic acid mine drainage was achieved through titrating the components of SAMD (Fe and Al salt solutions) and solutions of various Fe:Al mole ratios with different bases in air and N2, and comparing the SAMD-FAL system with these simple acids and bases. The FAL used in all experiments was produced from fresh fly ash collected at Arnot power station. The SAMD was prepared as a solution with a pH of 2.5 and containing 12.7 mmol/L Al, 10.9 mmol/L Fe and 40.8 mmol/L SO4. The characterisation of reaction solids was achieved by collecting the precipitates formed from the co-disposal of FAL and SAMD with Fe:Al ratios of 7.3, 0.8 and 2.5. From the titration experiments it was found that upscale potentiometric titrations of SAMD show buffer zones at pH values of 3.5, 4, 6 and 10 corresponding to Fe(III)precipitation, Al precipitation, Fe(II) hydrolysis and oxidation, and Al redissolution, respectively, while downscale potentiometric titrations with SAMD show buffer zones at pH values 12 – 11, 9 and 4.5, which correspond to Fe oxidation and precipitation, Al precipitation and Al re-dissolution, respectively. A high concentration of Al in the simulated AMD inhibited the crystallinity of the precipitates and resulted in a large quantity of SO4 being removed from solution, which suggests that an aluminium sulphate phase is precipitating, but it is not crystalline and cannot be identified by XRD. Titrations performed up-scale by adding FAL to AMD showed near-complete metal and substantial SO4 removal from solution. The characterisation of reaction solids by x-ray diffraction, infrared spectroscopy, thermal gravimetric and differential thermal analysis revealed that the precipitates consist of poorly crystalline, highly Al-substituted goethite and ferrihydrite with large amounts of SO4 included in the structure. Poorly crystalline bayerite appears at a high pH and high Al concentration, and calcite is present in precipitates made by adding SAMD to FAL. High surface charges of between 330 cmolc/kg positive and 550 cmolc/kg negative charge and potentially large specific surface areas between 7 and 236 m2/g suggest a strong potential for the precipitates to function as low-grade adsorbents in wastewater treatment. The similarity of these ochre precipitates to soil minerals implies that land disposal of the neutralised solids is also viable.
AFRIKAANSE OPSOMMING: Steenkool mynbou in SA produseer na benaming 200 ML suur mynwater per dag in die PWV area alleenlik, terwyl opwekking van elektrisiteit naastenby 27 Mt vliegas geproduseer het in 2001. ’n Groot aantal steenkoolmyne in SA word verbind met kragsentrales, waar hierdie twee strome afval, suur mynwater en vliegas, die kapasiteit het om mekaar te neutraliseer en die weg te baan vir gesamentlike wegdoening. Die doel van hierdie studie was om die reaksies wat plaasvind gedurende gesamentlike wegdoening van vliegas loog (VAL) en suur mynwater (SMW) te ondersoek, asook die neerslae wat mag vorm as gevolg van neutralisasie reaksies. Potensiometriese titrasies was gebruik om die neutralisering tussen Al:Fe-sout oplossings te ondersoek as nabootsing van SMW met gebruikmaking van alkaliese oplossings van Ca of Na hidroksied asook vars loog van VA. Die effektiwiteit van VA om metale en soute uit SMW te verwyder was getoets deur outleding van die geneutraliseerde water en modellering van die termodinamika. Neerslae berei uit groot-skaal sintetiese SMW en VAL en met gelyktydige storting by verskeie pH vlakke en Fe:Al verhoudings, was gekarakteriseer volgens samestelling, mineralogie en oppervlak eienskappe. Die eksperimentele neutralisering van sintetiese suur mynwater (SSMW) was gedoen deur titrering van die SSMW komponente en oplossings van verskeie Fe:Al molêre verhoudings met verskillende basisse in lug en N2, en vergelyking van SSMW-VAL sisteem met hierdie eenvoudige sure en basisse. Die VAL gebruik in alle eksperimente was geproduseer van vliegas verkry van die Arnot kragsentrale. Die SSMW was berei as ’n oplossing met ’n pH van 2.5 en bevat 12.7 mmol/L Al, 10.9 mmol/L Fe en 40.8 mmol/L SO4. Die karakterisering van vastestowwe uit die reaksie was gedoen deur die bemonstering van neerslae gevorm as gevolg van die gelyktydige wegdoening van VAL en SSMW met Al:Fe verhoudings van 7.3, 0.8 en 2.5.Die was waargeneem in die titrasie eksperimente dat hoër-skaal potensiometriese titrasie van SSMW buffersones, by pH waardes 3.5, 4, 6 en 10, ooreenstem met Fe(III) presipitasie, Al presipitasie, Fe(II) hidrolise en oksidasie, en Al her oplossing, terwyl laer skaal potensiometriese titrasie met SSMW buffer sones by pH waardes 12 - 11, 9 en 4.5 ooreenstem met Fe(III) presipitasie en oksidasie, Al presipitasie en heroplossing respektiewelik. ’n Hoë konsentrasie Al in die sintetiese SMW het kristalliniteit van die neerslae geïnhibeer en veroorsaak dat ’n hoeveelheid SO4 uit oplossing verwyder is, wat suggereer dat die AlSO4 fase neerslaan maar nie kristallyn is en gevolglik nie opgetel word met x-straal diffraksie nie. Titrasies gedoen by hoërskaal deur byvoeging van VAL tot SSMW, het feitlik volledige metaal en SO4 verwydering uit oplossing getoon. Die karakterisering deur x-straal diffraksie, infrarooispektroskopie, termies gravimetries en differentiële termiese analise, het getoon dat die presipitate bestaan uit swak kristallyne, hoë Al-gesubstitueerde goethiet en ferrihidriet met groot hoeveelhede SO4 vasgevang in die struktuur. Swak kristallyne bayeriet verskyn by hoë pH en hoë Al-konsentrasies en kalsiet is teenwoordig in neerslae gevorm deur byvoeging van SSMW tot VAL. Hoë oppervlakladings van tussen 330 cmolc/kg positief en 550 cmolc/kg negatiewe lading en ook potensieel groot spesifieke oppervlak van tussen 7 en 236 m2/g, dui op ’n sterk potensiaal vir neerslae om as laegraadse adsorbeermiddels in afvalwaterbehandeling gebruik te word. Die ooreenstemming in hierdie geelbruin neerslae met grond minerale, impliseer dat die land storting van geneutraliseerde vastestowwe ook lewensvatbaar is.

碩士
大同大學
化學工程學系(所)
107
The motivation of this research work is focused on synthesis and electro-catalytic characterization of Pd-based catalysts for anode materials in direct formic acid fuel cell application. 　　This study used transition metal oxides to modify the acid oxidized multi-walled carbon nanotubes (AO-MWCNTs) to avoid the direct influence of poisoning on the catalyst. The electrocatalytic performance of zirconia modified catalysts in different phases and the difference of carbon tube application in catalysts were discussed. 　　In this study, Pd catalysts were synthesized on different zirconia modified AO-MWCNTs by the photosynthesis method. Raman, FTIR and TGA were used to analyze the purity and surface morphology of the support. XRD, FESEM, and TEM were used to analyze the structure and surface morphology of the catalyst. The electrocatalytical performance was normalized by the experimental Pd weight percentage from ICP-OES. The electrical property of the catalysts was evaluated by ECSA, cyclic voltammetry (CV), CO stripping and CA. 　　The results show that tetragonal zirconia modified Pd catalysts prefer indirect dehydration pathway. While monoclinic zirconia modified one prefer direct dehydrogenation pathway.

碩士
大同大學
化學工程學系(所)
107
In the growing alternative energy sources, the fuel cell is a device that directly converts chemical energy into electrical energy. For direct formic acid fuel cells, the anodic catalyst palladium has recently been discussed. This study used conductive polymer Polyaniline (PANI) and Polypyrrole (PPY) to modified AO-MWCNTs. Three PANI and PPY to AO-MWCNTs proportions of 2:18:80, 5:15:80 and 10:10:80 were prepared as the catalyst supporters. The PANI and PPY modification is expected to suppress electron trapping by defect on the surface of AO-MWCNTs and enhance the conductivity of the Pd-based electrocatalysts. The palladium nanoparticles were synthesized on the carrier by synchrotron radiation synthesis reduction. The composition, structure and electrochemical properties of the products were determined by FTIR, RAMAN, EA, XRD, ICP, FE-SEM, TEM and CV. The results show that PANI and PPY synthesized by chemical method were successfully coated on AO-MWCNTs. The palladium nanoparticles synthesized by the synchrotron radiation synthesis reduction have particle size about 1-10 nm. Pd/(PPY/PANI-AO-MWCNTs-2/18/80) has the most stable electrocatalysis potential, and Pd/(PANI/AO-MWCNTs-20/80) has the best current density. It reveals that the PANI and PPY modification can enhance Pd catalytic ability of formic acid oxidation.

Alloys, intermetallic compounds and multi-metal oxides are generally made by traditional solid-state methods that often require melting or grinding/pressing powders followed by high temperature annealing (> 1000 degrees C) for days or weeks. The research presented here takes advantage of the fact that nanoparticles have a large fraction of their atoms on the surface making them highly reactive and their small size virtually eliminates the solid-solid diffusion process as the rate limiting step. Materials that normally require high temperatures and long annealing times become more accessible at relatively low-temperatures because of the increased interfacial contact between the nanoparticle reactants. Metal nanoparticles, formed via reduction of metal salts in an aqueous solution and stabilized by PVP (polyvinylpyrrolidone), were mixed into nanoparticle composites in stoichometric proportions. The composite mixtures were then annealed at relatively low temperatures to form alloy and intermetallic compounds at or below 600 degrees C. This method was further extended to synthesizing multi-metal oxide systems by annealing metal oxide nanoparticle composites hundreds of degrees lower than more traditional methods. Nanoparticles of Pt (supported or unsupported) were added to a metal salt solution of tetraethylene glycol and heated to obtain alloy and intermetallic nanoparticles. The supported intermetallic nanoparticles were tested as catalysts and PtPb/Vulcan XC-72 showed enhanced catalytic activity for formic acid oxidation while Pt3Sn/Vulcan XC-72 and Cu3Pt/y-Al2O3 catalyzed CO oxidiation at lower temperatures than supported Pt. Intermetallic nanoparticles of Pd were synthesized by conversion chemistry methods previously mentioned and were supported on carbon and alumina. These nanoparticles were tested for Suzuki cross-coupling reactions. However; the homocoupled product was generally favored. The catalytic activity of Pd3Pb/y-Al2O3 was tested for the Heck reaction and gave results comparable to Pd/y-Al2O3 with a slightly better selectivity. Conversion chemistry techniques were used to convert Pt nanocubes into Ptbased intermetallic nanocrystals in solution. It was discovered that aggregated clusters of Pt nanoparticles were capable of converting to FePt3; however, when Pt nanocubes were used the intermetallic phase did not form. Alternatively, it was possible to form PtSn nanocubes by a conversion reaction with SnCl2.

The first enantioselective, catalytic vinylogous Mukaiyama-Michael reaction of siloxyfurans with simple alpha,beta-unsaturated aldehydes has been reported using chiral imidazolidinones. This methodology provides access to enantioenriched gamma-butenolides, a privileged motif in organic synthesis. The utility of this organocatalytic Mukaiyama-Michael reaction was highlighted by the total syntheses of (--)-spiculisporic acid and (--)-5-epi-spiculisporic acid. Investigations into the total syntheses of cylindrocyclophanes A and F necessitated the development of a novel B-alkyl Suzuki cross-coupling of trimethylanilinium salts using a nickel(0) catalyst and bulky phosphine ligand. This methodology study revealed a very competitive nickel-catalyzed demethylation pathway, which produced dimethylaniline byproducts. A possible explanation for this side reaction is discussed. This technology was applied to a dimerization strategy for the C2-symmetric cylindrocyclophane F. Synthesis of a dimerization precursor included an enantioselective organocatalytic 1,4-addition of 3,5-dimethoxy-N,N-dimethylaniline into an alpha,beta-unsaturated aldehyde. However, the B-alkyl Suzuki cross-coupling was unsuccessful in promoting a dimerization. Next, the synthesis of cylindrocyclophane A was explored using an alternative ring-closing metathesis dimerization strategy. A dimerization precursor was to be assembled via the cross-coupling of trimethylanilinium salts with potassium (vinyl)trifluoroborate salts, whose syntheses featured an organocatalytic 1,4-conjugate reduction of a beta,beta-disubstituted enal. This cross-coupling strategy revealed olefin isomerization as a major side-reaction in the nickel-catalyzed Suzuki dimerization, making this route a non-productive approach to the natural product. Lastly, formal synthesis of cylindrocyclophane A was accomplished using (i) a nickel-catalyzed Stille cross-coupling of an activated vinyl stannane with a judiciously chosen trimethylanilinium salt and (ii) an asymmetric palladium-catalyzed allylic alkylation of an acyclic ketone. The latter represents the first example of application of the Pd2(dba)3/t-Bu-PHOX catalyst system to effect an asymmetric allylic alkylation on an acyclic system with good stereoselectivity. This route constituted a formal synthesis of cyclindrocyclophane A in eight linear steps, making it more efficient than the published route to the same advanced intermediate reported by Smith, which was synthesized in eleven steps.

碩士
國立清華大學
化學系
88
This thesis describes the formal asymmetric synthesis of 2-oxo-5a,8a-13,14,15,16-tetranorclerod-3-en-12-oic acid (54) and 6b-acetoxy-2-oxokolavenool (55) (Figure 1). The efficient synthesis of (R)-4-(2-benzyloxyethyl)-4-methyl-2-cyclohexenone [(-)-67], a common intermediate in a previously reported synthesis of both 54 and 55, in an asymmetric manner was the key concept in this approach. Towards this end, two approaches were investigated: enzymatic kinetic resolution and asymmetric synthesis via Meyer''s b-lactam approach to 4,4-disubstituted 2-cyclohexenones. In the first approach, kinetic resolution of a racemic mixture of 4-(2-benzyloxyethyl)-4-methyl-2-cyclohexenone as mediated by lipase AK did not result in a sufficiently high level of asymmetric resolution. However, during our investigations, we developed a new procedure to effectively resolve a racemic mixture of 2-phenylcyclohexanol (94) into its individual chiral forms quantitatively. In the approach using Meyer''s b-lactam ([2S-(2a,3b,8ab)]-(+)-hexahydro-3-(hydroxymethyl)-8a-methyl-2-phenyl-5H-oxazo-lo[3,2-a]pyridin-5-one, 87) as starting material, compound (-)-67 was realized in excellent optical and synthetically useful yields. The enantiomer of (-)-67, compound (+)-67, was also synthesized via this chemical approach in excellent optical and synthetically useful yields. Compound (+)-67 was further elaborated to Diels-Alder adducts (+)-70 and 92 containing the core decalin structure of cis-ent-clerodane natural products. The details of our investigations are described in this thesis.

Although α-keto carbocations have been demonstrated to be viable intermediates in solvolysis reactions, their applications in synthesis are scarce. These species can be considered to be equivalent to “reversed polarity” enolates and, as such, could be useful for the asymmetric formation of carbon-carbon and carbon-heteroatom bonds. In principle, facial selectivity in additions to α-keto carbocations may be induced using easily removed ester, amide, or imide chiral auxiliaries. Efforts to achieve such diastereoselective SN1 reactions of α-keto carbocations are described herein.

Chapter 2 of the thesis describes a highly efficient in situ method for the reduction of amides to aldehydes and aryl O-carbamates to phenols and other transformations involving hydrozirconations. The method, as a three-component-type reaction, involves in situ generation of the Schwartz reagent (Cp2Zr(H)Cl) from Cp2ZrCl2 and the reductant, LiAlH(O-t-Bu)3, and immediate reaction with a substrate. Substrates include aliphatic and aromatic tertiary amides which are reduced to aldehydes, aryl O-carbamates which are reduced to phenols, and alkynes which undergo other transformations via hydrozirconation. Compared to prior methods, this method has advantage in that reagents are inexpensive and stable, reaction times are short, and reaction temperatures are generally conveniently at room temperature. The use of the in situ method described herein instead of the requirement for the synthesis of the commercially available Schwartz reagent is estimated to provide more than 50% reduction in cost. Chapter 3 of the thesis describes the discovery and development of efficient and regioselective Ru-catalyzed amide-directed C-H, C-N, C-O activation/C-C bond forming reactions, ester-directed C-O activation/C-C bond forming reaction, and amide-directed C-O activation/hydrodemethoxylation reactions under a simple RuH2(CO)(PPh3)3/toluene catalytic system. Of these, the amide-directed C-H activation/cross coupling reaction proceeds well but uniquely on furan 3-amide substrates while the ester-directed C-O activation is effective on the 2-MeO-1-naphthoic acid methyl ester. On the other hand, the amide-directed C-N and C-O activation/coupling reactions are broadly applicable on benzamides and naphthamides. All of these achievements of directed C-H, C-N, C-O activation/coupling reactions complement and may supercede the DoM (directed ortho metalation)-cross coupling strategy, and establish the catalytic base-free DoM-cross coupling process at non-cryogenic temperature as a convenient, economical and green alternative. The new catalytic amide-directed ortho-hydrodemethoxylation reaction has potential value in links to aromatic electrophilic substitution and DoM chemistries. Furthermore, a new borylation reaction via Ru-catalyzed amide-directed C-H activation/C-B bond forming process is also reported herein.
Thesis (Ph.D, Chemistry) -- Queen's University, 2010-12-21 11:12:35.564