Structural changes and dynamic behaviour of vanadium oxide-based catalysts for gas-phase selective oxidations

Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

Glycerol oxidehydration to acrylic acid on complex mixed-metal oxides

The project of this Ph.D. thesis is based on a co-supervised collaboration between Università di Bologna, ALMA MATER STUDIORUM (Italy) and Instituto de Tecnología Química, Universitat Politècnica de València ITQ-UPV (Spain). This Ph.D. thesis is about the synthesis, characterization and catalytic testing of complex mixed-oxide catalysts mainly related to the family of Hexagonal Tungsten Bronzes (HTBs). These materials have been little explored as catalysts, although they have a great potential as multifunctional materials. Their peculiar acid properties can be coupled to other functionalities (e.g. redox sites) by isomorphous substitution of tungsten atoms with other transition metals such as vanadium, niobium and molybdenum. In this PhD thesis, it was demonstrated how it is possible to prepare substituted-HTBs by hydrothermal synthesis; these mixed-oxide were fully characterize by a number of physicochemical techniques such as XPS, HR-TEM, XAS etc. They were also used as catalysts for the one-pot glycerol oxidehydration to acrylic acid; this reaction might represent a viable chemical route to solve the important issue related to the co-production of glycerin along the biodiesel production chain. Acrylic acid yields as high as 51% were obtained and important structure-reactivity correlations were proved to govern the catalytic performance; only fine tuning of acid and redox properties as well as the in-framework presence of vanadium are fundamental to achieve noteworthy yields into the acid monomer. The overall results reported herein might represent an important contribution for future applications of HTBs in catalysis as well as a general guideline for a multifaceted approach for their physicochemical characterization.

Studio del comportamento meccanico di smalti porcellanati per substrati metallici

Composite porcelain enamels are inorganic coatings for metallic components based on a special ceramic-vitreous matrix in which specific additives are randomly dispersed. The ceramic-vitreous matrix is made by a mixture of various raw materials and elements and in particular it is based on boron-silicate glass added with metal oxides(1) of titanium, zinc, tin, zirconia, alumina, ecc. These additions are often used to improve and enhance some important performances such as corrosion(2) and wear resistance, mechanical strength, fracture toughness and also aesthetic functions. The coating process, called enamelling, depends on the nature of the surface, but also on the kind of the used porcelain enamel. For metal sheets coatings two industrial processes are actually used: one based on a wet porcelain enamel and another based on a dry-silicone porcelain enamel. During the firing process, that is performed at about 870°C in the case of a steel substrate, the enamel raw material melts and interacts with the metal substrate so enabling the formation of a continuous varying structure. The interface domain between the substrate and the external layer is made of a complex material system where the ceramic vitreous and the metal constituents are mixed. In particular four main regions can be identified, (i) the pure metal region, (ii) the region where the metal constituents are dominant compared with the ceramic vitreous components, (iii) the region where the ceramic vitreous constituents are dominant compared with the metal ones, and the fourth region (iv) composed by the pure ceramic vitreous material. It has also to be noticed the presence of metallic dendrites that hinder the substrate and the external layer passing through the interphase region. Each region of the final composite structure plays a specific role: the metal substrate has mainly the structural function, the interphase region and the embedded dendrites guarantee the adhesion of the external vitreous layer to the substrate and the external vitreous layer is characterized by an high tribological, corrosion and thermal shock resistance. Such material, due to its internal composition, functionalization and architecture can be considered as a functionally graded composite material. The knowledge of the mechanical, tribological and chemical behavior of such composites is not well established and the research is still in progress. In particular the mechanical performances data about the composite coating are not jet established. In the present work the Residual Stresses, the Young modulus and the First Crack Failure of the composite porcelain enamel coating are studied. Due to the differences of the porcelain composite enamel and steel thermal properties the enamelled steel sheets have residual stresses: compressive residual stress acts on the coating and tensile residual stress acts on the steel sheet. The residual stresses estimation has been performed by measuring the curvature of rectangular one-side coated specimens. The Young modulus and the First Crack Failure (FCF) of the coating have been estimated by four point bending tests (3-7) monitored by means of the Acoustic Emission (AE) technique(5,6). In particular the AE information has been used to identify, during the bending tests, the displacement domain over which no coating failure occurs (Free Failure Zone, FFZ). In the FFZ domain, the Young modulus has been estimated according to ASTM D6272-02. The FCF has been calculated as the ratio between the displacement at the first crack of the coating and the coating thickness on the cracked side. The mechanical performances of the tested coated specimens have also been related and discussed to respective microstructure and surface characteristics by double entry charts.

Sintesi e caratterizzazione di nanopolveri composite allumina-zirconia

Il presente lavoro di tesi riguarda la sintesi di nanopolveri allumina-zirconia, seguendo tre differenti metodologie (sintesi per coprecipitazione, sintesi con il metodo dei citrati, sintesi idrotermale assistita da microonde) e il trattamento termico (calcinazione) delle polveri ottenute, mediante tecniche di riscaldamento convenzionali ed alternative (microonde). Lo scopo del lavoro è consistito nell’individuare, tra le tecniche esaminate, quella più idonea e conveniente, per la preparazione di nanopolveri cristalline 95 mol% Al2O3 – 5 mol% ZrO2 e nell’esaminare gli effetti che la calcinazione condotta con le microonde, ha sulle caratteristiche finali delle polveri, rispetto ai trattamenti termici convenzionali. I risultati ottenuti al termine del lavoro hanno evidenziato che, tra le tecniche di sintesi esaminate, la sintesi idrotermale assistita da microonde, risulta il metodo più indicato e che, il trattamento termico eseguito con le microonde, risulta di gran lunga vantaggioso rispetto a quello convenzionale. La sintesi idrotermale assistita da microonde consente di ottenere polveri nano cristalline poco agglomerate, che possono essere facilmente disaggregate e con caratteristiche microstrutturali del tutto peculiari. L’utilizzo di tale tecnica permette, già dopo la sintesi a 200°C/2ore, di avere ossido di zirconio, mentre per ottenere gli ossidi di alluminio, è sufficiente un ulteriore trattamento termico a basse temperature e di breve durata (400°C/ 5 min). Si è osservato, inoltre, che il trattamento termico condotto con le microonde comporta la formazione delle fasi cristalline desiderate (ossidi di alluminio e zirconio), impiegando (come per la sintesi) tempi e temperature significativamente ridotti. L’esposizione delle polveri per tempi ridotti e a temperature più basse consente di evitare la formazione di aggregati duri nelle nanopolveri finali e di contrastare il manifestarsi di fenomeni di accrescimento di grani, preservando così la “nanostruttura” delle polveri e le sue caratteristiche proprietà.