Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.

Self‐cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Green factory as a factor of sustainability: the case of GM engine plant in Joinvile - SC

The new engine plant by General Motors (GM) in Joinville-SC, inaugurated on February 27th 2013, incorporates the most advanced automotive technology processes and broad compliance with environmental standards and energy efficiency. The initiatives implemented in this industrial plant include processes with 100% of recycled industrial waste (landfill free) and pioneer systems in energy efficiency and environmental protection, qualifying the plant to obtain the global certification of Leadership in Energy and Environmental Design (LEED). This industrial project reveals the strategic importance of the region and of Brazil in the growth of GM in the world, becoming a reference for studies and project evaluations of "green" factories in the automotive sector. The present study performs an exploratory research based on scientific publications, assessing the direct and indirect impacts on the business outcome, resulting from implementation of industrial serviceoriented sustainability of its operations, referred to in this article as "Green Factory”. We concluded that the adopted technologies focused on sustainability, study and development, represent a new step for the design of new plants and future expansions of the company in the region, combining low operating cost, low environmental impact and conservation of natural resources.

Biomass, quality traits and methane production of extensive grassland: biodiversity effects and sensor approaches

Energy policies around the world are mandating for a progressive increase in renewable energy production. Extensive grassland areas with low productivity and land use limitations have become target areas for sustainable energy production to avoid competition with food production on the limited available arable land resources and minimize further conversion of grassland into intensively managed energy cropping systems or abandonment. However, the high spatio-temporal variability in botanical composition and biochemical parameters is detrimental to reliable assessment of biomass yield and quality regarding anaerobic digestion. In an approach to assess the performance for predicting biomass using a multi-sensor combination including NIRS, ultra-sonic distance measurements and LAI-2000, biweekly sensor measurements were taken on a pure stand of reed canary grass (Phalaris aruninacea), a legume grass mixture and a diversity mixture with thirty-six species in an experimental extensive two cut management system. Different combinations of the sensor response values were used in multiple regression analysis to improve biomass predictions compared to exclusive sensors. Wavelength bands for sensor specific NDVI-type vegetation indices were selected from the hyperspectral data and evaluated for the biomass prediction as exclusive indices and in combination with LAI and ultra-sonic distance measurements. Ultrasonic sward height was the best to predict biomass in single sensor approaches (R² 0.73 – 0.76). The addition of LAI-2000 improved the prediction performance by up to 30% while NIRS barely improved the prediction performance. In an approach to evaluate broad based prediction of biochemical parameters relevant for anaerobic digestion using hyperspectral NIRS, spectroscopic measurements were taken on biomass from the Jena-Experiment plots in 2008 and 2009. Measurements were conducted on different conditions of the biomass including standing sward, hay and silage and different spectroscopic devices to simulate different preparation and measurement conditions along the process chain for biogas production. Best prediction results were acquired for all constituents at laboratory measurement conditions with dried and ground samples on a bench-top NIRS system (RPD > 3) with a coefficient of determination R2 < 0.9. The same biomass was further used in batch fermentation to analyse the impact of species richness and functional group composition on methane yields using whole crop digestion and pressfluid derived by the Integrated generation of solid Fuel and Biogas from Biomass (IFBB) procedure. Although species richness and functional group composition were largely insignificant, the presence of grasses and legumes in the mixtures were most determining factors influencing methane yields in whole crop digestion. High lignocellulose content and a high C/N ratio in grasses may have reduced the digestibility in the first cut material, excess nitrogen may have inhibited methane production in second cut legumes, while batch experiments proved superior specific methane yields of IFBB press fluids and showed that detrimental effects of the parent material were reduced by the technical treatment

Euphorbia tirucalli L.–Comprehensive Characterization of a Drought Tolerant Plant with a Potential as Biofuel Source

Of late, decrease in mineral oil supplies has stimulated research on use of biomass as an alternative energy source. Climate change has brought problems such as increased drought and erratic rains. This, together with a rise in land degeneration problems with concomitant loss in soil fertility has inspired the scientific world to look for alternative bio-energy species. Euphorbia tirucalli L., a tree with C3/CAM metabolism in leaves/stem, can be cultivated on marginal, arid land and could be a good alternative source of biofuel. We analyzed a broad variety of E. tirucalli plants collected from different countries for their genetic diversity using AFLP. Physiological responses to induced drought stress were determined in a number of genotypes by monitoring growth parameters and influence on photosynthesis. For future breeding of economically interesting genotypes, rubber content and biogas production were quantified. Cluster analysis shows that the studied genotypes are divided into two groups, African and mostly non-African genotypes. Different genotypes respond significantly different to various levels of water. Malate measurement indicates that there is induction of CAM in leaves following drought stress. Rubber content varies strongly between genotypes. An investigation of the biogas production capacities of six E. tirucalli genotypes reveals biogas yields higher than from rapeseed but lower than maize silage.

Produção de CDR a partir de resíduos industriais: caso de estudo da Recivalongo

A produção de combustível derivado de resíduos (CDR) resultou de uma decisão política que permitiu a instalação em Portugal de um significativo conjunto de processos, cuja avaliação técnico-económica e ambiental pode já ser feita. Este trabalho faz uma avaliação técnica e ambiental da linha de produção de CDR da Recivalongo. A avaliação técnica consistiu na análise dos caudais de material que entraram na linha de produção, na quantidade de CDR produzido, contabilizando também os gastos de recursos da linha (energia e materiais auxiliares). A avaliação da qualidade de CDR produzido a partir do ensaio laboratorial representou também uma parte muito significativa do trabalho produzido. A avaliação ambiental foi efetuada com base na metodologia da Avaliação de Ciclo de Vida (ACV). Os resultados obtidos permitiram concluir que o processo da Recivalongo transforma 69% do material de entrada, recuperando 2% em metais ferrosos e rejeitando para aterro a restante fração de 29%. As análises efetuadas ao CDR mostraram que apresenta um PCI compreendido entre 17 e 20 MJ/kg; o teor em cloro está compreendido entre 0,2 e 0,8% Conclui-se que neste processo o parâmetro mais difícil de controlar é o teor em cloro no CDR, pois existe uma grande diversidade de resíduos com grandes quantidades de cloro na sua constituição e que por muitas vezes são difíceis de identificar e/ou separar na primeira fase do tratamento dos resíduos. Da análise ciclo de vida efetuada à produção de CDR pode-se afirmar que esta operação de gestão de resíduos apresenta uma mais-valia quando comparada com a deposição dos resíduos em aterro, não sendo a diferença entre destinos tão significativa quanto o esperado. Desta avaliação pode concluir-se que a instalação operou muito abaixo da sua capacidade, sendo esta considerada uma das melhores linhas de produção de CDR a nível nacional.

Relações de cooperação em consórcios públicos de regiões metropolitanas: análises do CONDIAM/PB e consórcio grande Recife

With the disorganized decentralization occurred in Brazil after the 1988 Constitution, municipalities have risen to the level of federal entities. This phenomenon became known as "municipalism" also brought some negative effects such as low capacity financial, economic and political of these entities. In the face of this reality , the municipalities sought in models of collaborative features to address public policy issues ultrarregionais, one of these models are the Public Consortia. Characterized as the organization of all federal entities that aim to solve public policy implementation alone that they could not, or spend great resources for such. This reality of the municipalities have an aggravating factor when looking at the situation in Metropolitan Regions (MRs). This is because the RMs has a historical process of formation that does not encourage cooperation, since that were created top-down during the military regime. Furthermore, the metropolitan municipalities have significant power asymmetries, localist vision, rigidity earmarked revenues, different scenarios conurbation, difficulty standardization of concepts and others that contribute to the vision of low cooperation of these metropolitan areas. Thus, the problem of this work is in the presence of collaborative arrangements, such as the Public Consortia in metropolitan areas, which are seen as areas of low cooperation. To elucidate this research was used for analysis the cases of CONDIAM/PB and Consórcio Grande Recife/PE, because they are apparently antagonistic, but with some points of similarity. The cases has as foundation the Theory of Common Resources, which provides the possibility of collective action through the initiative of individuals. This theory has as its methodology for analyzing the picture IAD Framework, which proposes its analysis based on three axes: external variables, the arena of action and results. The nature of the method of this research was classified as exploratory and descriptive. For the stage of date analysis, was used the method of document analysis and content, Further than of separation of the cases according to theur especificities. At the end of the study, noted that the CONDIAM/PB was a strategy of municipal government of Joao Pessoa to attract funds from the Federal Government for the purpose of to build a landfill, and over the years the ideology of cooperation was left aside, the prevailing view localist municipalities. In the case of Consórcio Grande Recife/PE, members act with some degree of cooperation, especially the collaborative aspect of the region, however, still prevails with greater strength the power of the state of Pernambuco in the decisions and paths of the consortium. Thus, was conclude that the Public Consortia analyzed are an experience of collaborative arrangement, from the initiative of members, as the theory of common resources says, but has not actually signed as a practice of collective action to overcome the dilemmas faced by metropolitan areas