Estudo de catalisadores de Ni/ZnO promovidos com CeO2 aplicados em reações de reforma a vapor do etanol e acetona

A produção de energia é um dos grandes desafios deste século, principalmente com a necessidade no desenvolvimento de processos que utilizem preferencialmente fontes renováveis. Nesse contexto, é claro o interesse por pesquisas baseada no hidrogênio. Porém, os ganhos ambientais efetivos estão associados também à matéria-prima usada no processo de geração do hidrogênio, senso assim mais significativo quando do uso de fontes renováveis. No presente trabalho foi estudado o efeito da adição de diferentes teores de CeO2 em catalisadores de NiZnO, preparados pelo método da co-precipitação. Os catalisadores foram estudados frente à reação de reforma a vapor do etanol (RVE) para produção de H2, e no decorrer do trabalho foi pertinente incluir o estudo da reforma a vapor da acetona (RVA), como complemento dos estudos da RVE. Além disso, esta é uma molécula modelo para reforma a vapor do bio-óleo. Nos sistemas catalíticos sintetizados houve a formação da liga NiZn3, o que aparenta proporcionar um efeito sinérgico entre esses elementos. Observou-se um efeito altamente promotor do CeO2 com relação a diminuição do coque formado, devido a uma menor da formação da acetona, durante as etapas de reforma do etanol. O que consequentemente interferiu na produção de H2. O catalisador contendo 20% de CeO2 denominado NiZn20Ce apresentou um desempenho altamente promissor, pois de acordo com as análises de DRIFT, a presença do CeO2 levou a formação de espécies de formiato, o que consequentemente interferiu em uma menor formação de coque e maior produção de H2. Foi comprovado também que a natureza dos depósitos carbonáceos depende tanto do substrato utilizado quanto das etapas precursoras inicias que levarão a formação desse coque, sendo o ponto chave para um melhor desempenho do catalisador.

Catalisadores Ni/MgO-SiO2 aplicados na reação de reforma a vapor de glicerol

Catalisadores de Ni (10% em massa) suportado em matrizes mistas MgO-SiO2 foram aplicados na reação de reforma a vapor de glicerol. Os efeitos do teor de MgO como aditivo e do método de preparação foram avaliados frente às propriedades físico-químicas e texturais dos materiais; assim como à atividade, seletividade, estabilidade e formação de carbono na reforma a vapor do glicerol. Os catalisadores foram preparados com diferentes teores mássicos de MgO (10%, 30% e 50%) sobre SiO2 comercial, utilizando processo via seca (mistura física) e via úmida (impregnação sequencial com diferentes solventes: água, etanol e acetona). Foram utilizadas as técnicas de caracterização de espectroscopia de energia dispersiva de raios X, fisissorção de nitrogênio, difratometria de raios X, termogravimetria, difratometria de raios X in situ com O2, redução a temperatura programada com H2, difratometria de raios X in situ com H2, dessorção a temperatura programada com H2 e microscopia eletrônica de varredura. Foi observado que o Ni(II) interage de forma variada com os suportes com diferentes teores de MgO, e que a polaridade do solvente de impregnação utilizado no processo de preparação influencia as propriedades dos catalisadores. A fim de verificar a atividade, seletividade e deposição de carbono; os catalisadores foram testados na reação de reforma a vapor de glicerol a 600oC, por um período de 5h e razão molar água:glicerol de 12:1. Após as reações, os catalisadores foram novamente submetidos às análises de termogravimetria, difratometria de raios X e microscopia eletrônica de varredura, visando a caracterização dos depósitos de carbono obtidos durante o processo catalítico. Os catalisadores de matrizes mistas se mostraram ativos e apresentaram seletividades similares para os produtos gasosos CH4, CO e CO2, além de um alto rendimento em H2. Observou-se que a adição de MgO no suporte, aumentou a dispersão do Ni(II) no material, que por sua vez, influenciou na quantidade de carbono depositado ao longo da reação. A polaridade do solvente de impregnação também teve influência na dispersão metálica, sendo que, quanto menor a polaridade do solvente, maior foi a dispersão obtida no catalisador, e menor a deposição de carbono na reação. O material que apresentou o melhor desempenho catalítico frente ao rendimento de H2 e à deposição de carbono, foi o catalisador preparado com 30% de MgO com etanol como solvente de impregnação.

Dignity and the Eighth Amendment: A New Approach to Challenging Solitary Confinement

The use of solitary confinement in U.S. prisons and jails has come under increasing scrutiny. Over the past few months, Supreme Court Justice Anthony Kennedy all but invited constitutional challenges to the use of solitary confinement, while President Obama asked, “Do we really think it makes sense to lock so many people alone in tiny cells for 23 hours a day for months, sometime for years at a time?” Even some of the most notorious prisons and jails, including California’s Pelican Bay State Prison and New York’s Rikers Island, are reforming their use of solitary confinement because of successful litigation and public outcry. Rovner suggests that in light of these developments and “the Supreme Court’s increasing reliance on human dignity as a substantive value underlying and animating constitutional rights,” there is a strong case to make that long-term solitary confinement violates the constitutional right to freedom from cruel and unusual punishment.

Gasification and pyrolysis of Posidonia oceanica in the presence of dolomite

In the present work, a very detailed study of the reforming of syngas produced in the decomposition of Posidonia oceanica is done. The effect of the presence of different amounts of dolomite is analyzed. Also pyrolysis is studied, in nitrogen atmosphere, and gasification in the presence of air, oxygen and different amounts of steam. A detailed discussion on formation and destruction of tars is done. Furthermore, the effect of the heating rate in the decomposition and the residence time of the evolved gases are discussed. Syngas with ratio H2/CO from 0.3 to ca. 3 can be obtained from this interesting material. Marine species (microalgae) are usually studied with the aim of cultivating them for gas or oil production, but in this paper we draw attention to the possibility of using a natural resource with a very small impact in the ecosystem.

Gasification and Pyrolysis of Posidonia oceanica in the Presence of Dolomite

Resumen del póster presentado en Symposium on Renewable Energy and Products from Biomass and Waste, CIUDEN (Cubillos de Sil, León, Spain), 12-13 May 2015

Approximation to EU Technical Standards with and without the Promise of Membership: the Cases of Slovakia and Ukraine. EU Diplomacy Paper 02/2013

This paper aims to identify the extent to which the non-promise of membership of the European Union (EU) precludes the motivation of Ukraine as European Neighbourhood Policy country to adopt EU policies in the field of market access, namely technical standards and regulations. Its approximation approach is compared to the fast-tracked accession of Slovakia, which was driven by a clear-cut membership promise. Furthermore, the paper elaborates whether the conclusion of an Association Agreement between the EU and Ukraine, including a Deep and Comprehensive Free Trade Agreement, provides sufficient incentives for Ukraine to continue reforming its quality infrastructure in order to gain access to the Single European Market. Finally, scenarios of possible developments of EU-Ukraine relations are deliberated in the context of the EU-Ukraine-Russia triangle. The paper argues that market access provides sufficient stimulus for third countries to adhere to EU technical standards – even in the absence of a clear and credible promise of future EU membership. Yet, in the case of Ukraine, the country’s relations with Russia appear to compete with its EU approximation process, resulting for the time being in Ukraine attempting to pursue a balanced dual cooperation with both the EU and Russia.

Extending working life in Finland. CEPS Working Document No. 387, 22 November 2013

This report reviews national and private initiatives to allow the elderly to continue their participation in the Finnish labour market and provides an analysis of the labour market and living conditions of seniors. We are interested in how those over 50 can be engaged in various forms of employment and lifelong learning. We find strong evidence that Finland generally provides good institutional conditions for active ageing. The quick and early ageing process was tackled by the fundamental pension reform that already prolonged retirement substantially and will probably facilitate later retirement as the attitudes concerning retirement change. On the other hand, Finland still seems to lag behind the other Nordic welfare states, has considerable problems in providing the same health conditions to low educated people in physically demanding occupations and could - – with respect to family pension in particular – invest further efforts in reforming the pension system. While many of the reforms Finland has conducted seem to be favourable and transferable to other European countries that still face the steepest phases of ageing in their societies, a reluctance towards changing attitudes that we observe in Finland, shows that organizing active ageing is a long-term project.

Net Neutrality and Mandatory Network-Sharing: How to disconnect the continent. CEPS Policy Brief No. 309, 18 December 2013

A lively debate emerged on the proposed “Connected Continent” legislative package presented by the European Commission in September 2013. The package contains a proposed rule on the ‘open Internet’, which was heavily discussed in European Parliament hearings in early December. This commentary argues that while the proposed rule is in principle balanced and appealing, it is utterly impractical due to the enormous uncertainty that its application would entail. At the same time, the rule is very far from what neutrality proponents have argued for almost a decade: rather than the place for internet freedom, it would transform the Web into a place requiring constant micro-management and tutoring of user behaviour. Both arguments lead to the conclusion that the current proposal should be at once reformed and analysed under a more holistic lens. On the one hand, Europe should launch an ambitious project for the future, converged infrastructure by mobilising resources and reforming rules to encourage investment into ubiquitous, converged, ‘always on’ connectivity. On the other hand, enhanced legal certainty for broadband investment could justify a more neutrality-oriented approach to traffic management practices on the Internet. The author proposes a new approach to Internet regulation which, altogether, will lead to a more balanced and sustainable model for the future, without jeopardising user freedom.

Labour Market Reforms and Current Account Imbalances: Beggar-thy-neighbour policies in a currency union? CEPS Working Document No. 399/September 2014

Member countries of the Economic and Monetary Union (EMU) initiated wide-ranging labour market reforms in the last decade. This process is ongoing as countries that are faced with serious labour market imbalances perceive reforms as the fastest way to restore competitiveness within a currency union. This fosters fears among observers about a beggar-thy-neighbour policy that leaves non-reforming countries with a loss in competitiveness and an increase in foreign debt. Using a two-country, two-sector search and matching DSGE model, we analyse the impact of labour market reforms on the transmission of macroeconomic shocks in both non-reforming and reforming countries. By analysing the impact of reforms on foreign debt, we contribute to the debate on whether labour market reforms increase or reduce current account imbalances.

Financing the EU Budget: Moving forward or backwards? CEPS Paperback

Often described as complex, opaque and unfair, the EU budget financing system is an ‘unfinished journey’. One of the most critical issues is that EU revenue, drawn from the cashbox of national taxation, remains intangible to the general public. The nature of the EU as a union of states and their nationals makes the visibility of EU revenue unavoidable. The political sustainability of a move that would put the legitimacy of EU revenue at the forefront of public discussion will depend on the EU institutions and member states’ ability to demonstrate that EU funds can achieve results that are truly beyond member states’ reach. In this, his third, CEPS book on the EU budget, Gabriele Cipriani assesses the current system of financing the EU budget against the criteria of simplicity, transparency, equity and democratic accountability and offers two possible options for reforming the EU revenue system. He finds that the value-added tax (VAT) is a natural choice for funding the EU budget, through a dedicated EU VAT rate as part of the national VAT and designed as such in fiscal receipts, whose use as a means for raising EU citizens’ awareness could be encouraged already in the current arrangements.

European Neighbourhood Policy Package - Conclusions for the Eastern Partners. OSW Commentary No. 78, 2012-05-25

In 2011 the European Union began a process aimed at reforming its policy on the Eastern and Southern Neighbourhood. The change in circumstances in neighbouring countries following the Arab Spring, along with the lack of significant progress regarding Eastern Europe’s integration with the EU, formed the main driving force behind this process. The prime objective of the changes to the European Neighbourhood Policy (ENP) was the need to introduce new incentives for partner countries to modernise and integrate more closely with the EU Another aim was to increase the flexibility of EU instruments (by adapting them to the specific context of each partner state). One year later, on 15 May 2012, the European Commission and the EU High Representative for Foreign Affairs and Security Policy published the European Neighbourhood Policy Package which reported on the progress made in the implementation of the ENP over the preceding year and set out the aims and Action Plans for 20131. An analysis of the outcomes of changes made to the EU policy towards Eastern Europe and the South Caucasus suggests that the aim of the revision was aimed more at addressing the changing political landscape in the region rather than at the implementation of a substantial reform of the neighbourhood policy. The ENP is largely based on bureaucratic procedures (the negotiation of bilateral agreements, the implementation of support programmes). These have only a limited capacity to bring about lasting change in the region, as has been exemplified by the deterioration of democratic standards in a number of countries; this was highlighted in EU’s own reports. This problem is particularly clear in the case of Ukraine; until recently it was seen as the leader of European integration but is now raising much concern due to a deterioration in the state of democracy there. EU instruments have a limited influence on the situation in Eastern Partnership countries and the region’s significance on the EU’s agenda is falling (the priority is now given to counteracting the economic crisis, and prominence in the neighbourhood policy has been given to the Southern Mediterranean). In response to this EU policy on Eastern Europe will focus to a larger extent on technical and sectoral cooperation.

Turkey: has the AKP ended its winning streak? OSW Commentary No. 117, 2013-10-07

Since the conservative Justice and Development Party (AKP) took power in Turkey in 2002, it has enjoyed a constant winning streak: it won each election (with a support level of 49.83% in 2011), subordinated the army (which had de facto stood above the civilian government) and was reforming the country. The situation in the country was stable (especially when compared to the crises and restlessness in the 1990s), the economy was booming, Turkey’s position in regional politics was strengthening, and Ankara’s significance on the international arena was growing. This encouraged the ruling class to make long-term plans, leading up to the hundredth anniversary of the republic in 2023. In the coming decade, Turkey governed by the AKP was to become one of the global economic and political centres, a full member of the EU and at the same time a political and economic leader in the Middle East. However, the negative trends in the situation both domestically (mass public protests, the deadlocked Kurdish issue and the unsuccessful attempt to amend the constitution) and abroad (the war in Syria and the coup in Egypt) seen over the past few months have laid bare the limitations of the AKP’s rule and have affected the government’s democratic mandate, prestige and credibility on the international arena, as well as peace and order and domestic security. When compared to the beginning of 2013, the way the situation will develop in Turkey is at this moment definitely less predictable; and the possible scenarios include both relative peace (however, with socio-political tension present in the background) and the threat of destabilisation. Therefore, although the AKP will still remain the sole major political force, this party will have to face challenges which will decide not only its political future but also the directions the country will be developing in. However, a comprehensive solution of the accumulated problems and a simple return to the status quo ante, convenient to the government, seem unlikely in the foreseeable future.

The Economics of Subsidies for R&D: The Intrinsic Difficulty of Determining Optimum Subsidies and Implications for Reform of EU State Aid Rules on R&D. Bruges European Economic Research (BEER) Papers 26/February 2013

The European Commission is reforming state aid rules. An important element of the reform is to prevent the granting of excessive subsidies. This paper shows that the determination of the optimum subsidy for research is difficult. What appears to be the socially optimum level of research effort depends on the benchmark of comparison and whether this benchmark is the situation before subsidies or the situation after subsidies. In the presence of asymmetric information, policy makers should induce firms to reveal their true costs and should grant subsidies to the relatively more efficient firms by allocating subsidies not on a first-come-first- serve basis but through a competitive process. However, competitive selection of subsidy recipients is not a panacea as it may not be possible to be effectively used in all cases and for all research programmes. This is because in principle public subsidies should support those programmes with the largest value for society, rather than with the lowest costs. Although this paper focuses on R&D, its findings are relevant to any subsidy whose aim is to remedy market failure caused by positive externalities.

What Future for the Eurozone? Combining Discipline, Solidarity and Institutional Reforms. European Policy Brief No. 27, March 2014

This Policy Brief discusses the challenges that await policymakers in reforming the EMU. A balance between discipline and solidarity will have to be found, while institutional reforms should improve the eurozone’s legitimacy and efficiency. The key decisions on EMU reforms will have to be made during the 2014-2019 parliamentary term, as the window of opportunity for major reforms is likely to be closed afterwards.

Disentangling the Reform Gridlock: Higher Education in Germany. CES Germany & Europe Working Papers, No. 02.7, 2002

For more than a decade, bemoaning the many roadblocks to reforming important aspect of German politics has become commonplace. Explanations emphasize formal and informal veto points, such as the role of political institutions and the lack of elite and societal support for reform initiatives. Against this background, I was interested in factors that place policy issues on the political agenda and follow up with concrete courses of action; i.e., in factors that lead to a disentangling of the reform gridlock. I emphasize the importance of agenda setting in the emergence of higher education reform in Germany. Globalization, European integration and domestic pressures combined to create new pressures for change. In response, an advocacy coalition of old and new political actors has introduced a drawn-out and ongoing process of value reorientation in the direction of competition, including international competition, and greater autonomy. The result has been a burst of activities, some moderate, some more far-reaching in their potential to restructure German higher education.