Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

(De)colonization through topophilia: Marjorie Kinnan Rawlings’s life and work in Florida

(De)colonization Through Topophilia: Marjorie Kinnan Rawlings’s Life and Work in Florida attempts to reveal the author’s intimate connection to and mental growth through her place, namely the Cross Creek environs, and its subsequent effect on her writing. In 1928, Marjorie Kinnan Rawlings and her first husband Charles Rawlings came to Cross Creek, Florida. They bought the shabby farmhouse on Cross Creek Road, trying to be both, writers and farmers. However, while Charles Rawlings was unable to write in the backwoods of the Florida Interior, Rawlings found her literary voice and entered a symbiotic, reciprocal relationship with the natural world of the Cracker frontier. Her biographical preconditions – a childhood spent in the rural area of Rock Creek, outside of Washington D. C. - and a father who had instilled in her a sense of place or topophilia, enabled her to overcome severe marriage tensions and the hostile climate women writers faced during the Depression era. Nature as a helping ally and as an “undomesticated”(1) space/place is a recurrent motif throughout most of Rawlings’s Florida literature. At a time when writing the American landscape/documentary and the extraction of the self from texts was the prevalent literary genre, Marjorie Kinnan Rawlings inscribed herself into her texts. However, she knew that the American public was not yet ready for a ‘feminist revolt’, but was receptive of the longtime ‘inaudible’ voices from America’s regions, especially with regard to urban poverty and a homeward yearning during the Depression years. Fusing with the dynamic eco-consciousness of her Cracker friends and neighbors, Rawlings wrote in the literary category of regionalism enabling her to pursue three of her major aims: an individuated self, a self that assimilated with the ‘master narratives’ of her time and the recognition of the Florida Cracker and Scrub region. The first part of this dissertation briefly introduces the largely unknown and underestimated writer Marjorie Kinnan Rawlings, providing background information on her younger years, the relationship toward her family and other influential persons in her life. Furthermore, it takes a closer look at the literary category of regionalism and Rawlings’s use of ‘place’ in her writings. The second part is concerned with the ‘region’ itself, the state of Florida. It focuses on the natural peculiarities of the state’s Interior, the scrub and hammock land around her Cracker hamlet as well as the unique culture of the Florida Cracker. Part IV is concerned with the analysis of her four Florida books. The author is still widely related to the ever-popular novel The Yearling (1938). South Moon Under (1933) and Golden Apples (1935), her first two novels, have not been frequently republished and have subsequently fallen into oblivion. Cross Creek (1942), Rawlings’s last Florida book, however, has recently gained renewed popularity through its use in classes on nature writers and the non-fiction essay but it requires and is here re-evaluated as the author’s (relational) autobiography. The analysis through place is brought to completion in this work and seems to intentionally close the circle of Rawlings’s Florida writings. It exemplifies once more that detachment from place is impossible for Rawlings and that the intermingling of life and place in literature, is essential for the (re)creation of her identity. Cross Creek is therefore not only one of Rawlings’s greatest achievements; it is more importantly the key to understanding the author’s self and her fiction. Through the ‘natural’ interrelationship of place and self and by looking “mutually outward and inward,”(2) Marjorie Kinnan Rawlings finds her literary voice, a home and ‘a room of her own’ in which to write and come to consciousness. Her Florida literature is not only product but also medium and process in her assessment of her identity and self. _____________ (1) Alaimo, Stacy. Undomesticated Ground: Recasting Nature as Feminist Space (Ithaca: Cornell UP, 2000) 23. (2) Libby, Brooke. “Nature Writing as Refuge: Autobiography in the Natural World” Reading Under the Sign of Nature. New Essays in Ecocriticism. Ed. John Tallmadge and Henry Harrington. (Salt Lake City: The U of Utah P, 2000) 200.

Capability of a space-based space surveillance system to detect and track objects in GEO, MEO and LEO orbits

In this paper we present the results from the coverage and the orbit determination accuracy simulations performed within the recently completed ESA study “Assessment Study for Space Based Space Surveillance (SBSS) Demonstration System” (Airbus Defence and Space consortium). This study consisted in investigating the capability of a space based optical sensor (SBSS) orbiting in low Earth orbit (LEO) to detect and track objects in GEO (geosynchronous orbit), MEO (medium Earth orbit) and LEO and to determinate and improve initial orbits from such observations. Space based systems may achieve better observation conditions than ground based sensors in terms of astrometric accuracy, detection coverage, and timeliness. The primary observation mode of the proposed SBSS demonstrator is GEO surveillance, i.e. the systematic search and detection of unknown and known objects. GEO orbits are specific and unique orbits from dynamical point of view. A space-based sensor may scan the whole GEO ring within one sidereal day if the orbit and pointing directions are chosen properly. For an efficient survey, our goal was to develop a leak-proof GEO fence strategy. Collaterally, we show that also MEO, LEO and other (GTO,Molniya, etc.) objects would be possible to observe by the system and for a considerable number of LEO objects to down to size of 1 cm we can obtain meaningful statistical data for improvement and validation of space debris environment models

Space-based space surveillance and tracking demonstrator: mission and system design

This paper presents the capabilities of a Space-Based Space Surveillance (SBSS) demonstration mission for Space Surveillance and Tracking (SST) based on a micro-satellite platform. The results have been produced in the frame of ESA’s "Assessment Study for Space Based Space Surveillance Demonstration Mission" performed by the Airbus Defence and Space consortium. The assessment of SBSS in an SST system architecture has shown that both an operational SBSS and also already a well- designed space-based demonstrator can provide substantial performance in terms of surveillance and tracking of beyond-LEO objects. Especially the early deployment of a demonstrator, possible by using standard equipment, could boost initial operating capability and create a self-maintained object catalogue. Furthermore, unique statistical information about small-size LEO debris (mm size) can be collected in-situ. Unlike classical technology demonstration missions, the primary goal is the demonstration and optimisation of the functional elements in a complex end-to-end chain (mission planning, observation strategies, data acquisition, processing, etc.) until the final products can be offered to the users and with low technological effort and risk. The SBSS system concept takes the ESA SST System Requirements into account and aims at fulfilling SST core requirements in a stand-alone manner. Additionally, requirements for detection and characterisation of small-sizedLEO debris are considered. The paper presents details of the system concept, candidate micro-satellite platforms, the instrument design and the operational modes. Note that the detailed results of performance simulations for space debris coverage and cataloguing accuracy are presented in a separate paper “Capability of a Space-based Space Surveillance System to Detect and Track Objects in GEO, MEO and LEO Orbits” by J. Silha (AIUB) et al., IAC-14, A6, 1.1x25640.

Mobilities and Pottery Production Archaeological and Anthropological Perspectives

Our workshop aims at a deeper understanding of various itineraries of pottery and dif-ferent forms of human mobilities in which pottery is relevant, bringing together archae-ological and anthropological perspectives. For thousands of years, pottery has been an important part of many societies’ material culture and therefore a major research topic in both disciplines. In past and present societies the material existence of ceramic vessels is informed by various movements across time and space but also by periods of stasis: from the mo-ment of their production until their exclusion from daily practices, either disposed as waste, excluded as funerary objects or stored as collectibles. In their seemingly endless material durability, ceramic vessels might outlive their human producers, distributors or consumers and travel farther and longer. Still they are embedded in the regimes of human mobility, ranging from daily subsistence-based mobility to long-term migrations. In such processes, pottery shifts between spatial, temporal, social, economic and cultural contexts. Thereby ceramic vessels are appropriated and integrated in new contexts of action and meaning, sometimes leading to material transformations. This workshop takes place in the context of our archaeological research project „Mobili-ties, Entanglements and Transformations in Neolithic Societies on the Swiss Plateau (3900-3500 BC)“ to which our PhDs are connected. We address the above outlined topic by analysing the production of pottery. Based on dendrochronologically dated settle-ments between 3900 and 3500 BC, two regional pottery styles and their local variations are well known, Pfyn and Cortaillod. The vessels share the same habitus and were made of clays and temper deriving from the settlements’ surroundings. However, some vessels specific to other pottery styles are also present on the sites. They are characteristic for pottery styles known from more or less far off regions (Michelsberg, Munzingen or Néo-lithique Moyen Bourguignon). Some of them were travelling objects, as their non local raw materials show. Others seem to have been produced locally, pointing to long-term mobility and a change of residence from neighbouring social groups.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Documentation, profile descriptions and analytical results of loes profiles from Bavaria, southern Germany

This study investigates the landscape evolution and soil development in the loess area near Regensburg between approximately 6000-2000 yr BP (radiocarbon years), Eastern Bavaria. The focus is on the question how man and climate influenced landscape evolution and what their relative significance was. The theoretical background concerning the factors that controlled prehistoric soil erosion in Middle Europe is summarized with respect to rainfall intensity and distribution, pedogenesis, Pleistocene relief, and prehistoric farming. Colluvial deposits , flood loams, and soils were studied at ten different and representative sites that served as archives of their respective palaeoenvironments. Geomorphological, sedimentological, and pedological methods were applied. According to the findings presented here, there was a high asynchronity of landscape evolution in the investigation area, which was due to prehistoric land-use patterns. Prehistoric land use and settlement caused highly difIerenciated phases of morphodynamic activity and stability in time and space. These are documented at the single catenas ofeach site. In general, Pleistocene relief was substantially lowered. At the same time smaller landforms such as dells and minor asymmetric valleys filled up and strongly transformed. However, there were short phases at many sites, forming short lived linear erosion features ('Runsen'), resulting from exceptional rainfalls. These forms are results of single events without showing regional trends. Generally, the onset of the sedimentation of colluvial deposits took place much earlier (usually 3500 yr BP (radiocarbon) and younger) than the formation of flood loams. Thus, the deposition of flood loams in the Kleine Laaber river valley started mainly as a consequence of iron age farming only at around 2500 yr BP (radiocarbon). A cascade system explains the different ages of colluvial deposits and flood loams: as a result of prehistoric land use, dells and other minor Pleistocene landforms were filled with colluvial sediments. After the filling of these primary sediment traps , eroded material was transported into flood plains, thus forming flood loams. But at the moment we cannot quantify the extent ofprehistoric soil erosion in the investigation area. The three factors that controlled the prehistoric Iandscapc evolution in the Ioess area near Regensburg are as follows: 1. The transformation from a natural to a prehistoric cultural landscape was the most important factor: A landscape with stable relief was changed into a highly morphodynamic one with soil erosion as the dominant process of this change. 2. The sediment traps of the pre-anthropogenic relief determined where the material originated from soil erosion was deposited: either sedimentation took place on the slopes or the filled sediment traps of the slopes rendered flood loam formation possible. Climatic influence of any importance can only be documented as the result of land use in connection with singular and/or statistic events of heavy rainfalls. Without human impact, no significant change in the Holocene landscape would have been possible.

Survey on integration of Applied Geology and Geomorphology in Civil Engineering curricula in the framework of the European Higher Education Area (EHEA) by using practical trips

The engineer must have sufficient theoretical knowledge to be applied to solve specific problems, with the necessary capacity to simplify these approaches, and taking into account factors such as speed, simplicity, quality and economy. In Geology, its ultimate goal is the exploration of the history of the geological events through observation, deduction, reasoning and, in exceptional cases by the direct underground exploration or experimentation. Experimentation is very limited in Geology. Reproduction laboratory of certain phenomena or geological processes is difficult because both time and space become a large scale. For this reason, some Earth Sciences are in a nearly descriptive stage whereas others closest to the experimental, Geophysics and Geochemistry, have assimilated progress experienced by the physics and chemistry. Thus, Anglo-Saxon countries clearly separate Engineering Geology from Geological Engineering, i.e. Applied Geology to the Geological Engineering concepts. Although there is a big professional overlap, the first one corresponds to scientific approach, while the last one corresponds to a technological one. Applied Geology to Engineering could be defined as the Science and Applied Geology to the design, construction and performance of engineering infrastructures in and field geology discipline. There has been much discussion on the primacy of theory over practice. Today prevails the exaggeration of practice, but you get good workers and routine and mediocre teachers. This idea forgets too that teaching problem is a problem of right balance. The approach of the action lines on the European Higher Education Area (EHEA) framework provides for such balance. Applied Geology subject represents the first real contact with the physical environment with the practice profession and works. Besides, the situation of the topic in the first trace of Study Plans for many students implies the link to other subjects and topics of the career (tunnels, dams, groundwater, roads, etc). This work analyses in depth the justification of such practical trips. It shows the criteria and methods of planning and the result which manifests itself in pupils. Once practical trips experience developed, the objective work tries to know about results and changes on student’s motivation in learning perspective. This is done regardless of the outcome of their knowledge achievements assessed properly and they are not subject to such work. For this objective, it has been designed a survey about their motivation before and after trip. Survey was made by the Unidad Docente de Geología Aplicada of the Departamento de Ingeniería y Morfología del Terreno (Escuela Técnica Superior de Ingenieros de Caminos, Canales y Puertos, Universidad Politécnica de Madrid). It was completely anonymous. Its objective was to collect the opinion of the student as a key agent of learning and teaching of the subject. All the work takes place under new teaching/learning criteria approach at the European framework in Higher Education. The results are exceptionally good with 90% of student’s participation and with very high scores in a number of questions as the itineraries, teachers and visited places (range of 4.5 to 4.2 in a 5 points scale). The majority of students are very satisfied (average of 4.5 in a 5 points scale).

The Influence of Space Layout, Technology and Teaching Approach on Student Learning: An Architectural Technology Perspective

Some would argue that there is a need for the traditional lecture format to be rethought in favour of a more active approach. However, this must form part of a bipartite strategy, considered in conjunction with the layout of any new space to facilitate alternative learning and teaching methods. With this in mind, this paper begins to examine the impact of the learning environment on the student learning experience, specifically focusing on students studying on the Architectural Technology and Management programme at Ulster University. The aim of this study is two-fold: to increase understanding of the impact of learning space layout, by taking a student centered approach; and to gain an appreciation of how technology can impact upon the learning space. The study forms part of a wider project being undertaken at Ulster University known as the Learning Landscape Transition Project, exploring the relationship between learning, teaching and space layout. Data collection was both qualitative and quantitative, with use of a case study supported by a questionnaire based on attitudinal scaling. A focus group was also used to further analyse the key trends resulting from the questionnaire. The initial results suggest that the learning environment, and the technology within it, can not only play an important part in the overall learning experience of the student, but also assist with preparation for the working environment to be experienced in professional life.

Place but not Date of Birth Influences the Development and Emergence of Athletic Talent in American Football

The purpose of this study was to examine the birthplace and relative age effects in National Football League (NFL) players. The place and date of birth of NFL players in the United States were analyzed with Monte Carlo simulations to determine if either factor was predictive of the probability of reaching the elite level in this sport. Consistent with previous findings on professional North American athletes in baseball, ice hockey, basketball, and golf, players born in cities with populations of less than 500,000 were significantly over-represented in the NFL, whereas players born in cities with populations over 500,000 were significantly under-represented. Unlike many other sports, no relative age effects were found for the NFL. Small cities, in particular, appeared to possess characteristics that facilitate the development and/or emergence of athletic talent in American football. Possible psychosocial factors mediating the birthplace effect are discussed as are implications for the development of sporting expertise.

Small Town Downtown Revitalization: Applying the Main Street Approach to the towns of Perth and Carleton Place, Ontario

The downtown main street of small towns is traditionally the economic, cultural, and social heart of the community, thereby requiring particular attention from planners and researchers alike. Considering modern threats to main streets including suburban sprawl and "big box" development, revitalization strategies are essential to ensuring longevity and vitality of small towns’ cores, in terms of economy, built environment, heritage, and identity. The Main Street Approach was established to mitigate challenges by providing a revitalization tool-kit for small Canadian towns, focusing on organization, marketing and promotion, economic and commercial development, and design and physical improvements. To better understand existing municipal tools for downtown revitalization in Ontario, a comparative analysis of the towns of Carleton Place and Perth's policies was conducted using the four pillars of the Main Street Approach as benchmark for best practice, and recommendations for other small towns to better incorporate revitalization policies were suggested.

Topex/Poseidon, a United States/France mission : oceanography from space : the oceans and climate.

"Mission to Planet Earth."

Microgravity : a new tool for basic and applied research in space /

Mode of access: Internet.

Space measurements survey: Instruments and spacecraft, October 1957-March 1965.

Mode of access: Internet.