Studio dell'interazione di etanolo con catalizzatori TiO2-CeOx.

Due to the limited availability of natural oil and the harmful effects of its usage, the industry has focused in searching for sustainable types of raw materials for the production of chemicals. The bioethanol, obtained by fermentation of biomass, has gained particular importance in recent years both as a biofuel, and as a “building block” molecule because it can be considered as a starting reagent to obtain other added value chemical compounds, such as ethylene, acetaldehyde, butadiene and ethyl acetate. The goal of this research was the study of the interaction of ethanol with catalysts based on TiO2-CeOX. Since the electronic properties have implications on the catalytic activity, the idea was to understand if the TiO2-CeOX systems have different reactivity from that of ceria and rutile alone, or an intermediate between them. The study was focused on the characterization of the adsorbed species on the catalysts surface after ethanol adsorption through an in-situ spectroscopic technique (DRIFTS) that allowed us to extract information that could be helpful for the understanding of the processes at the molecular level. The mass spectrometry was used to monitor on-line the desorbed products. Furthermore, reactivity tests in a flow reactor were performed, in order to verify the catalytic behavior of the samples in conditions which are more similar to those applied at an industrial scale. The samples showed to behave in different way depending on the conditions used and the thermal treatment. The particular behavior of the mixed samples with respect to the single oxides is interpreted for each case according to the spectroscopic information collected.

The applicability of non-local LCI data for LCA

This study evaluated how applicable European Life Cycle Inventory (LCI) data are to assessing the environmental impacts of the life cycle of Brazilian triple superphosphate (TSP). The LCI data used for the comparison were local Brazilian LCI data, European LCI data in its original version from the ecoinvent database and a modified version of the European LCI data, which had been adapted to better account for the Brazilian situation. We compared the three established datasets at the level of the inventory as well as for their environmental impacts, i.e. at the level of Life Cycle Environmental Assessment (LCIA). The analysis showed that the European LCIs (both the original and the modified ones) considered a broader spectrum of background processes and environmental flows (inputs and outputs). Nevertheless, TSP production had in all three cases similar values for the consumption of the main raw materials. The LCIA results obtained for the datasets showed important differences as well. Therefore we concluded that the European data in general lead to much higher environmental impacts than the Brazilian data. The differences between the LCIA results obtained with the Brazilian and the European data can be basically explained by the methodological differences underlying the data. The small differences at the LCI level for selected inputs and outputs between the Brazilian and the European LCIs from ecoinvent indicate that the latter can be regarded as applicable for characterizing the Brazilian TSP.

EFFETS DE L’INCORPORATION D’ADJUVANTS MINÉRAUX SUR LES PROPRIÉTÉS DE CIMENTS GÉOPOLYMÈRES A BASE DE SCORIES VOLCANIQUES

Volcanic ashes are raw materials from geological deposits with a range of chemical compositions. When combined with suitable alkali activators they can be converted to geopolymers cement at ambient temperature. In this work we have investigated the possibility of use bauxite and oyster shells as mineral admixture in volcanic ashes, to enhance the properties of geopolymers synthesized. Different methods of analyses such as Fourier Transform Infrared spectroscopy (FTIR), X-ray diffractometry (XRD), and Scanning Electron Microscopy (SEM) were used to assess the variation of setting time, linear shrinkage and 28 days compressive strength of geopolymers paste. The bauxite and the oyster shells were characterized using inductively coupled plasma (ICP-AES), thermal analyses (DSC/ATG), FTIR and X-ray diffractometry. The results of these analyses has showed that bauxite and oyster shells are respectively source of Al2O3 and of CaO, and can compensate the deficiencies of these oxides in volcanic ashes. Adding mineral admixture dissolve slowly in high alkaline medium. Addition of about 20% of bauxite or 10% of oyster shells is seen to decrease the setting time respectively from 415 to 275 min and 195 min. Linear shrinkage decrease with percentage of bauxite or of oyster shells added. Efflorescence is reduced by adding 10% of bauxite. 28 days compressive strength of geopolymeric materials increase respectively for 4.77 and 7.52% for 10% of bauxite or 20% of oyster shells added. More than these percentage additive has a deleterious effect on compressive strength due to crystalized mineralogical phases of the admixture.

Elaboration et caractérisation de ciments géopolymères à base de scories volcaniques

Two types of volcanic ashes referenced as ZD (volcanic ashes from Djoungo) and ZG (volcanic ashes from Galim) were collected from two Cameroonian localities. They were characterized (chemical and mineralogical compositions, amorphous phase content, particle size distribution and specific surface area) and used as raw materials for the synthesis of geopolymer cements at ambient temperature of laboratory (24 ± 3 °C). The synthesized products were characterized by determining their setting time, linear shrinkage and compressive strength, X-ray Diffraction, Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. The mineralogical composition, the amorphous phase content, the particle size distribution, the specific surface area of the volcanic ashes as well as the mass ratio of the alkaline solution (sodium silicate / sodium hydroxide) were the main parameters which influenced the synthesis of geopolymers with interesting characteristics at ambient temperature (24 ± 3 °C). The volcanic ashes (ZD) whose mineralogical composition contained anhydrite, low amorphous phase content and low specific surface area led to long setting times. Moreover, its products swelled and presented cracks due to the formation of ettringite and these resulted in low compressive strengths (7 to 19 MPa). The volcanic ashes (ZG) containing high amounts of amorphous phase and high specific surface area led geopolymers with setting times between 490 and 180 minutes and compressive strength between 7 and 50 MPa at ambient temperature of laboratory. The properties of geopolymers were improved when elaborated with a mixture of volcanic ashes and metakaolin (ZD–MK and ZG–MK). For geopolymers obtained from ZD–MK, the setting time was between 500 and 160 minutes while it was between 220 and 125 minutes for geopolymers obtained from ZG–MK. The compressive strength greatly increased between 23 and 68 MPa and 39 and 64 MPa for geopolymers obtained from ZG –MK and ZD–MK respectively. A comparative study of the properties of mixtures of metakaolin–alumina and volcanic ash–alumina based geopolymers shows that metakaolin is a good source of Al2O3 and SiO2 and which highly reactive with alkaline solution and produces geopolymers with better characteristics compared to volcanic ash based–geopolymer. The properties of volcanic ash–based geopolymer were also improved when amorphous alumina was incorporated into the volcanic ash. This additive is used to compensate the deficiencies in Al2O3 content in the volcanic ash. Compare to when volcanic ash is used alone 20 to 40 % incorporation of this additive corresponded to increases of the compressive strength by 18.1 % for metakaolin-alumina based-geopolymers and by 32.4 % for volcanic ash-based geopolymers.

Effects of adding Bauxite and Oyster shell on the properties of metakaolin-based geopolymer cements

This work has investigated the possibility of use bauxite and oyster shell as mineral admixtures,to enhance the properties of metakaolin-based geopolymer cements. Raw materials(metakaolin, bauxite and oyster shell) were characterized in the first time by determination of their chemical and mineralogical compositions, particles size distribution, specific surface area, thermal analysis and then in the second time use to synthesized geopolymers. Different methods of analysis such as Fourier Transform Infrared spectroscopy(FTIR), X-Ray Diffractometry (XRD), and Scanning Electron Microscopy (SEM) were used to assess the variation of setting time, linear shrinkage and 28 days compressive strength of geopolymer pastes. The results of these analysis has showed that bauxite and oyster shells are source of Al2O3 and CaO respectively, and also contain crystalline phases. The geopolymers obtained by mixing metakaolin and bauxite have their setting time between 235 and 420min and their compressive strength between 40 and 57MPa ; for those obtained by mixing metakaolin and oyster shell the setting time is between 330 and 485min and compressive strength between 40 and 58MPa . The addition of a moderate amount (20% by mass) of bauxite or oyster shell led to improve the compressive strength of a metakaolin-based geopolymer of 43% (metakaolin-bauxite-based geopolymers) and 45% (metakaolin-oyster shell-based geopolymers) and decrease the linear shrinkage. More than 20% mineral additive has a deleterious effect on compressive strength and increase the setting time. Keywords: Metakaolin ; Bauxite ; Oyster shell ; synthesis ; Optimization; Geopolymer cements.

DEVELOPMENT OF POROUS CONCRETE GEOPOLYMER USING HYDROGEN PEROXIDE AS BLOWING AGENT.

Metakaolin and volcanic ashes respectively called MK and ZG were used as aluminosilicate raw materials for the synthesis of porous geopolymers. The hydrogen peroxide was used as a blowing agent. The geopolymer prepared were characterized by Spectroscopy Fourier Transform Infrared (SFTI), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and the determination of some physical properties such as bulk density, total porosity, volume shrinkage, compressive strength and thermal conductivity was also carried out. The presence of pores in the geopolymer obtained is function of the percentage of hydrogen peroxide added, causing the concomitantly decrease in compressive strength, apparent density and thermal conductivity. The use of hydrogen peroxide as a blowing agent gave some thermal insulation properties to these geopolymers which could be close to the properties of some commercial insulation materials.

The Intersection of Economics and Politics in a Small OPEC Country: the Case of Ecuador, 1990 - March 2014

Today, crude oil remains a vital resource all around the world. This non-renewable resource powers countries worldwide. Besides serving as an energy source, crude oil is also the most important component for different world economies, especially in developing countries. Ecuador, a small member of the OPEC oil cartel, presents a case where its economy is oil dependent. A great percentage of the country¿s GDP and government¿s budget comes from oil revenues. Ecuador has always been a primary exporter of raw materials. In the last centuries, the country experienced three important economic booms: cacao, bananas, and, ultimately, crude oil. In this sense, the country has not been able to fully industrialize and begin to export manufactured goods, i.e., Ecuador suffers from the Dutch disease. The latter has deterred Ecuador from achieving broad-based economic development. Given crude oil¿s importance for the Ecuadorian economy, the government has always tried to influence the oil industry in search of profits and benefits. Therefore, this thesis, explores the question: how and to what extent have political interventions affected the oil industry in Ecuador from 1990 until March 2014? In general, this thesis establishes an economic history context during the last twenty-four years, attempting to research how political interventions have shaped Ecuador¿s oil industry and economy. In the analysis, it covers a period where political instability prevailed, until Rafael Correa became president. The thesis examines Ecuador¿s participation in OPEC, trying to find explanations as to why the country voluntarily left the organization in 1992, only to rejoin in 2007 when Correa rose to power. During the ¿Revolución Ciudadana¿ period, the thesis researches reforms to the Law of Hydrocarbons, variations in the relations with other nations, the controversy surrounding the Yasuní-ITT oil block, and the ¿Refinería del Pacífico¿ construction. The thesis is an Industrial Organization detailed case study that analyzes, updates, and evaluates the intersection of economics and politics in Ecuador¿s crude oil industry during the last 24 years. In this sense I have consulted past theses, newspaper articles, books, and other published data about the petroleum industry, both from a global and Ecuadorian perspective. In addition to published sources, I was able to interview sociologists, public figures, history and economics academics, and other experts, accessing unique unpublished data about Ecuador¿s oil industry. I made an effort to collect information that shows the private and public side of the industry, i.e., from government-related and independent sources. I attempted to remain as objective as possible to make conclusions about the appropriate Industrial Organization policy for Ecuador¿s oil industry, addressing the issue from an economic, social, political, and environmental point of view. I found how Ecuador¿s political instability caused public policy to fail, molding the conduct and market structure of the crude oil industry. Throughout history, developed nations have benefited from low oil prices, but things shifted since oil prices began to rise, which is more beneficial for the developing nations that actually possess and produce the raw material. Nevertheless, Ecuador, a victim of the Dutch disease due to its heavy reliance on crude oil as a primary product, has not achieved broad-based development.

Batch scheduling in process industries: an application of resource-constrained project scheduling

The paper deals with batch scheduling problems in process industries where final products arise from several successive chemical or physical transformations of raw materials using multi–purpose equipment. In batch production mode, the total requirements of intermediate and final products are partitioned into batches. The production start of a batch at a given level requires the availability of all input products. We consider the problem of scheduling the production of given batches such that the makespan is minimized. Constraints like minimum and maximum time lags between successive production levels, sequence–dependent facility setup times, finite intermediate storages, production breaks, and time–varying manpower contribute to the complexity of this problem. We propose a new solution approach using models and methods of resource–constrained project scheduling, which (approximately) solves problems of industrial size within a reasonable amount of time.

Itineraries of pottery: a mixed methods approach to mobility

Neolithic wetland sites in the Swiss Plateau provide an extraordinary database for the study of mobilities, entanglements and transformations in material culture. Based on dendrochronologically dated settlements 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 local raw materials. However, some vessels specific to other pottery styles are also present in the sites. By focusing on itineraries of vessels and shifts in pottery knowledge, their appropriation in different contexts and the resulting material entanglements, we want to approach the multiple regimes of mobility: At Lake Constance - known for Pfyn pottery - specific Michelsberg vessels like tulip beakers and lugged jars occur in small numbers. These travelling objects were produced with exogenous raw materials and transported to the sites from Southern Germany. At Concise (Lake Neuchâtel) besides the local Cortaillod pottery the whole repertoire of NMB pottery, characteristic for Eastern France, was also produced. Further cases from the same space-time frame point to other regimes of mobility. In our two PhD-projects we compare pottery practices - styles, techniques, raw materials - from over 20 key sites in the region. Based on Bourdieu’s reflexive anthropology, we apply different qualitative and quantitative archaeological and archaeometrical methods, thus striving for a deeper understanding of habitus and the transformative potential of moving people, objects and ideas on local and regional scales and related social contexts.

Pottery as an indication of mobilities?

Pottery is one of the most common and stylistically differentiated sources in prehistoric archaeology. This might be the reason why it served as a waste projection surface for archaeological notions about culture, identity, and mobility in the past. As we do not have access to emic categorisations of Neolithic societies we focus on contexts of practice in which pottery was incorporated. It is the moment of production, which left some of the clearest traces on the vessels. Different ways of using raw materials, specific techniques, and characteristic pottery styles can be observed. We understand them as a result of habitus, as socially shared internalized schemes, patterns and habits in pottery production. Taking this as a staring point, two main pottery groups can be differed on the Swiss Plateau between 3900 and 3500 BC: the Mediterranean influenced Cortaillod pottery in Western Switzerland and the Danubian influenced Pfyn pottery in North-Eastern Switzerland. These pottery styles were not only entangled to some degree. Furthermore, in some settlements vessels made in “foreign” styles - Michelsberg, Munzingen, Néolithique Moyen Bourguignon - are present too. Some of them were travelling objects, as their nonlocal raw materials show. Others were locally made, indicating long-term mobility of their producers. To analyse these phenomena of mobilites and entanglements in our PhDs we plan to apply different archaeological and archaeometrical methods, thus striving for a deeper understanding of the transformative potential of moving people, objects and ideas in Neolithic societies on the Swiss Plateau.

Rendimiento de aceite de colza cultivada bajo riego : Mendoza (Argentina)

En el 2010 será obligatorio cortar en un 5% los combustibles de origen fósil (gasoil y naftas) con biocombustibles (biodiesel y bioetanol). La principal materia prima para elaborar biodiesel son los aceites vegetales. Cada región tiene ventajas comparativas para producir alguna oleaginosa. En Cuyo, una de las limitantes para la producción agrícola es la disponibilidad de agua, fundamentalmente en verano, cuando demandan este recurso los cultivos tradicionales de la región. En este contexto, se estudió el rendimiento del cultivo de colza, oleaginosa de ciclo invernal, en el oasis Norte de la región de Cuyo, con el objetivo de valorar su aptitud para proveer aceite. Se probaron tres cultivares en tres fechas de siembra (abril, mayo y junio), durante los ciclos 2005 y 2006. Las siembras de abril y mayo rindieron más que la de junio y estuvieron asociadas a mayor duración de ciclo del cultivo. No hubo diferencias de porcentaje de aceite de las semillas entre tratamientos, que osciló entre el 48 y 49%. El rendimiento de aceite por ha superó los 1500 kg en las siembras de abril y mayo y estuvo algo por debajo en las de junio.

Tecnología cerámica : estudios experimentales sobre la cerámica del sitio arqueológico San Ignacio (Noroeste de Mendoza)

El propósito de este trabajo es explorar la disponibilidad de materias primas que pudieron ser utilizadas en el proceso de manufactura de la cerámica gris del sitio arqueológico San Ignacio, en el Valle de Potrerillos, ubicado al Norte de la provincia de Mendoza (640 dC). Se pretende, además, reproducir las técnicas de producción y cocción cerámica, a fin de obtener un producto de características análogas a las de la colección estudiada. La metodología utilizada presentó las siguientes etapas: recolección de materiales arcillosos; caracterización de las propiedades físicas en estado crudo; análisis químicos; desarrollo experimental de cocción y ensayos post-cocción de los mismos. Los productos obtenidos muestran una buena estructura y sinterización, aunque no se logró una atmósfera completamente reductora con este tipo de combustible.

Extracción y análisis de pectinas a partir de arándano (Vaccinium corymbosum L.) cv. O'Neall

El arándano (Vacinium corymbosum) es un fruto muy apreciado debido a sus propiedades nutricionales, bajo valor energético y alto contenido de antioxidantes. Su remanente no exportable es destinado a la industria local para la elaboración de zumos, siendo una fuente potencial de pectinas. El presente estudio tuvo como objetivos: medir la influencia del pH 2,0; 2,75 y 3,36 natural y el tiempo de calentamiento entre 60 y 90 minutos a 90°C, sobre la extracción de pectina de arándano por medio de una hidrólisis ácida; evaluar la calidad de la pectina mediante el grado de esterificación; elaborar y evaluar desde el aspecto sensorial las gelatinas provenientes de pectinas extraídas a 35°, 50° y 65°Brix. El mayor rendimiento de pectina, 0,93% (p/p), se obtuvo a pH 2,0 y en 90 minutos. El grado de esterificación no superó el 50% en la mayoría de los tratamientos, clasificando las pectinas como de "bajo metoxilo". Los geles elaborados a 50°Brix tuvieron un mayor nivel de aceptabilidad por los panelistas, clasificándolos como "me gusta levemente". En relación con el atributo sensorial color de los geles elaborados, fue evaluado por los panelistas como "pálido", dado el leve color de las pectinas utilizadas.

Producción de agrocombustibles : ¿Territorios objetivos o territorios posibles?

Desde de la colonización los territorios de América Latina y de Africa fueron puestos al servicio de las metrópolis. La globalización del capitalismo financiero sigue el mismo patrón, deslocalizando la producción de agrocombustibles y concentrando el capital en las transnacionales agrarias. Recorremos cinco mitos que buscan legitimar esta producción y abordamos dos estudios de caso (Guatemala y Senegal) que ponen en evidencia la utilización de los territorios objetivos perjudicando las poblaciones indígenas y fundamentalmente las mujeres. El artículo finaliza con una reflexión sobre el pasaje de los territorios objetivos a Territorios Posibles, de la mano de la Inteligencia Territorial

Agroindústria familiar : Um mecanismo de estímulo à especialização das atividades na propriedade rural?

Family agroindustry has been considered by several authors as an important reproduction alternative for family-based agriculture. However, this production process, which includes primary (production of raw-materials) and secondary (industrialization of production) activities, is generating a general concern. Can agroindustry, by promoting non-agricultural income for farmers, cause a reduction or, in extreme cases, an extinction of agricultural production in farm estates developing industrialization activities for selling in markets (family agroindustries)? In this sense, the purpose of this research was to analyse whether agroindustry can promote specialisation in family-based farm estates, or whether it is a form of economic diversification, being merely an activity similar to those developed in farm estates before the emergence of this process. The empirical study was conducted in 45 family agroindustries of sugarcane derivatives located in the Northeast of Rio Grande do Sul (Brazil).