A utilização de briquetes de misturas de carvão fóssil e biomassa em substituição ao coque como agente redutor pode contribuir para a diminuição das emissões de CO2 à atmosfera no processo de redução de minério de ferro. O fenômeno do amolecimento e fluidificação do carvão fóssil durante o aquecimento permite que o mesmo absorva certa quantidade de materiais inertes à coqueificação durante o tratamento térmico. O objetivo deste trabalho é correlacionar o efeito das principais variáveis de processo de fabricação (temperatura e tempo de tratamento térmico, tamanho de partícula dos componentes, porosidade e proporção de carvão vegetal e carvão fóssil) sobre as propriedades obtidas (resistência mecânica e reatividade ao CO2) de briquetes compostos de misturas de carvão fóssil e carvão vegetal, para uso na indústria siderúrgica. Briquetes de dois formatos diferentes foram preparados em matriz cilíndrica e em maquina briquetadeira e tratados termicamente em forno vertical aquecido com resistência elétrica sob atmosfera de nitrogênio. A resistência à compressão dos briquetes foi analisada em função das seguintes variáveis: proporção de carvão fóssil e carvão vegetal, taxa de aquecimento do tratamento térmico e tamanho de partícula dos carvões. A reatividade ao CO2 dos briquetes tratados termicamente foi analisada em função das seguintes variáveis: temperatura de ensaio e vazão de CO2. Foram comparados os resultados obtidos de ambos os formatos de briquetes. Com o aumento da proporção de carvão vegetal nos briquetes cilíndricos de biocoque, a densidade aparente e a resistência à compressão após tratamento térmico aumentaram para as misturas contendo 5, 10 e 15% de carvão vegetal. A partir dessa composição (15% de carvão vegetal) tanto a densidade final quanto a resistência à compressão apresentaram diminuição. Encontrou-se que tanto os briquetes cilíndricos a verde quanto os briquetes tratados termicamente apresentam perda de resistência mecânica com o aumento do tamanho de partícula do carvão fóssil. Os melhores valores de resistência à compressão foram obtidos em briquetes feitos com carvão fóssil em mistura de 15% em peso de carvão vegetal, tamanho de partícula abaixo de 0,044 mm, tratados termicamente a 1100°C durante 8 horas. Com o aumento na adição de carvão vegetal nos briquetes compostos de carvão fóssil e carvão vegetal, observou-se um aumento da reatividade do biocoque ao CO2. As micrografias dos briquetes tratados termicamente mostraram que a textura dos briquetes tende a ser mais homogênea com aumento de carvão vegetal de madeira na mistura. Os briquetes de biocoque fabricados em briquetadeira permitiram a ampliação do processo de fabricação de briquetes a uma escala laboratorial maior e mostraram a viabilidade industrial na fabricação do biocoque. Encontrou-se que a adição de carvão vegetal de madeira na mistura influencia diretamente na resistência a compressão e a reatividade ao CO2, devido a diferentes fatores como a composição das cinzas da madeira, a diminuição da fluidez devido à ação do inerte na mistura a carbonizar, a formação de uma estrutura porosa dentro da matriz carbonosa. Não encontrou-se correlação entre o índice de alcalinidade dos briquetes e sua reatividade ao CO2. / The substitution of metallurgical coke by briquetted mixtures of coal and biomass as a reducing agent can lower the emissions of greenhouse gases (CO2) in the iron and steelmaking industry. The thermal plasticity of the coking coal can be used to absorb an amount of inert materials during heat treatment. The objective of this study is to correlate the effect of the main processes variables (heat treatment temperature and duration, particle size of the materials, porosity and coal and charcoal ratio) on the properties (compressive strength and CO2 reactivity) of briquetted mixtures of coal and charcoal. Two types of briquettes were produced, one in a cylindrical die and another in a laboratory briquetting machine. The briquettes were heat treated in a vertical electrical furnace under nitrogen atmosphere. The compressive strength of the briquettes was analyzed as a function of the following variables: coal and charcoal ratio, heating rate and particle size. The CO2 reactivity of the heat treated briquettes was analyzed as a function of the following variables: temperature and CO2 flow. For the cylindrical briquettes, the increase of charcoal (5, 10, 15 wt%) in the coal-charcoal mixtures caused an increase on the bulk density and on the compressive strength of the heat treated briquettes. Above 15 wt% of charcoal in the mixtures, the bulk density and the compressive strength decreased. It was found out that both green and heat treated briquettes had a decrease in compressive strength with the increase of the coal particle size. Optimum results of compressive strength were obtained in the briquettes with 15 wt% of charcoal, particle size <0.044 mm, heat treatment temperature of 1100°C for 8 hours. The increase in charcoal proportion caused an increase in the CO2 reactivity of the briquettes. The SEM micrographs of the heat treated briquettes showed that the texture of the briquettes tend to be more homogeneous with the increase of charcoal in the mixture. The properties of the briquettes produced in the laboratorial briquetting machine showed that a large scale production could be viable. Also, it was found out that the addition of wood charcoal in the mixture directly affects the compressive strength and the CO2 reactivity of the briquettes due to factors such as: the ashes composition, the decrease in fluidity because of the inert material in the mixture, the formation of a porous structure inside the carbon matrix. It was not found a relation between the alkalinity index and the CO2 reactivity in the briquettes.

Submitted by Otavio Augusto Lopes (otavio.augusto.lopes@accenture.com) on 2013-07-22T19:14:45Z No. of bitstreams: 1 Dissertacao_OTAVIOLOPES_VFINAL22072013.pdf: 1475230 bytes, checksum: 6c63a8b848e961e6694369632a1572b3 (MD5) / Approved for entry into archive by Suzinei Teles Garcia Garcia (suzinei.garcia@fgv.br) on 2013-07-22T19:33:55Z (GMT) No. of bitstreams: 1 Dissertacao_OTAVIOLOPES_VFINAL22072013.pdf: 1475230 bytes, checksum: 6c63a8b848e961e6694369632a1572b3 (MD5) / Made available in DSpace on 2013-07-22T19:37:12Z (GMT). No. of bitstreams: 1 Dissertacao_OTAVIOLOPES_VFINAL22072013.pdf: 1475230 bytes, checksum: 6c63a8b848e961e6694369632a1572b3 (MD5) Previous issue date: 2013-06-28 / This study brings an analysis on how bioenergy could have each more a relevant role on the Brazil electric matrix. This study also demonstrates the grower and processing context of sugarcane in Brazil, with a focus on the bioenergy generation. It also shares the current technology scenario for bioenergy generation at the industry and right after presents the combined cycle as an opportunity to improve the way of bioenergy generation. In the end of the study a feasibility analysis with a qualitative approach is shared demonstrating what needs to be done from different perspectives to reach the future scenario and related benefits. The study shares the current sector challenges on bioenergy generation and some actions to enable the sector to take advantage of new technology and other improvements. / Este estudo apresenta uma análise de como a bioeletricidade sucroenergética pode ter um papel cada vez mais importante na matriz energética brasileira. O estudo mostra o contexto da produção e processamento de cana de açúcar no Brasil, colocando ênfase no processo de geração de energia elétrica. As opções de tecnologia em uso atualmente para a geração na indústria de açúcar e bioenergia são discutidas e, em seguida, apresenta o modelo de ciclo combinado baseado no consumo de gás proveniente da gaseificação de resíduos de cana de açúcar como oportunidade de melhoria de eficiência para o processo. Ao final o estudo apresenta uma avaliação qualitativa de viabilidade buscando demonstrar o que precisa ser feito para se alcançar os resultados com o modelo futuro. Para tal o estudo irá buscar demonstrar os atuais desafios do setor de Bioenergia na indústria de cana de açúcar e projetará ações em diferentes atores desse mercado para a viabilização de adoção de novas tecnologias.

Abstract The blast furnace – basic oxygen furnace route remains the most utilised process route in the production of steel worldwide. Coke is the main fuel of the blast furnace process, however, coke producers and blast furnace operators are facing significant challenges due to increased demands on coke quality and decrease of prime coking coals. The estimation of coke performance in the industrial process through accurate laboratory analyses is of increasing importance. In this doctoral thesis, the aim was to study phenomena related to coke properties and its analysis methods in blast furnace simulating conditions. A new method was introduced to measure the hot strength of coke using a Gleeble 3800 thermomechanical simulator. The hot strengths of industrial cokes were determined at various temperatures and several coke properties, which were believed to affect hot strength, were determined. The effect of H₂ and H₂O in the blast furnace shaft gas were determined in relation to coke reactivity, threshold temperature, and the gasification mechanism. The results obtained by this thesis show that the Gleeble device is suitable for study of coke hot strength. The coke strength was significantly decreased for all three coke grades at temperatures of 1600 °C and 1750 °C when compared to room temperature or 1000 °C. The deformation behaviour of coke was fragile up to 1000 °C, but became at least partially plastic at 1600 °C, and the plasticity further increased at 1750 °C. Notable changes were observed in the deformation behaviour between coke grades at high temperatures. The presence of H₂ and H₂O in the BF shaft gas strongly increased coke reactivity and changed the reaction mechanism of coke to be more surface centric in a specific temperature range. The reactivity of coke in the conditions 100 vol-% CO₂ did not directly correlate with reactivity in a simulated blast furnace shaft gas, which suggest that the widely utilised CRI test does not accurately estimate coke reactivity in the industrial blast furnace process. / Tiivistelmä Masuuni – konvertteri yhdistelmä on edelleen käytetyin prosessireitti teräksen tuotantoon ympäri maailman. Koksi on masuunin tärkein polttoaine. Koksintuottajat ja masuunioperaattorit ovat suurten haasteiden edessä johtuen koksin kasvaneista laatuvaatimuksista ja parhaiden koksautuvien kivihiilten ehtymisestä. Koksin suoriutumisen arviointi masuunin olosuhteissa tarkoilla laboratorioanalyyseillä on yhä merkittävämmässä roolissa. Tässä väitöskirjassa tavoitteena oli tuottaa uutta tietoa koksin ominaisuuksista ja sen analyysimenetelmistä simuloiduissa masuunin olosuhteissa. Uusi metodi esitettiin koksin kuumalujuuden määrittämiseksi Gleeble 3800 termomekaanisella simulaattorilla. Teollisten koksilaatujen kuumalujuuksia määritettiin eri lämpötiloissa ja useita koksin mitattiin, joilla uskottiin olevan vaikutus kuumalujuuteen. Lisäksi työssä tutkittiin masuunin kuilun kaasuatmosfäärissä H2 ja H2O kaasujen vaikutusta koksin kemialliseen reaktiivisuuteen, kaasuuntumisen kynnyslämpötilaan ja reaktiomekanismiin. Tässä työssä esitetyt tulokset osoittavat että Gleeble soveltuu koksin kuumalujuuden määritykseen. Koksin lujuus aleni merkittävästi kaikilla kolmella koksilaadulla kuumennettaessa 1600 ja 1750 °C lämpötiloihin verrattuna huoneenlämpötilaan tai 1000 °C lämpötilaan. Koksin muodonmuutos oli haurasta aina 1000 °C lämpötilassa, mutta muuttui osittain plastiseksi 1600 °C lämpötilassa ja plastisuus kasvoi kun lämpötilaa nostettiin 1750 °C:een. Huomattavia eroja havaittiin eri koksilaatujen muodonmuutoskäyttäytymisessä korkeissa lämpötiloissa. H₂ ja H₂O kaasujen läsnäolo kuilun kaasuatmosfäärissä kasvatti voimakkaasti koksin reaktiivisuutta ja muutti kaasuuntumismekanismia pintakeskisemmäksi rajatulla lämpötila-alueella. Koksin reaktiivisuus 100 % CO₂ kaasussa ei korreloinut suoraan simuloidun masuunin kuilun kaasuatmosfäärin kanssa. Tämä tulos indikoi sitä että maailmalla yleisesti käytetty CRI testi ei ennusta tarkasti koksin reaktiivisuutta masuunissa.

Abstract Gasification is an energy conversion method for the utilisation of biomass for obtaining energy (heat and power). In the gasification process carbon residue is formed as a waste. For improving the cost-effectiveness of the gasification process the utilisation of this waste is important and the present legislation also creates requirements for the utilisation of waste material. Activated carbon is typically used for purification of water, for example, wastewaters as well as gaseous emissions. Consequently, commercial activated carbon is fairly expensive and its preparation is energy consuming. However, this inhibits sometimes its widespread use in wastewater treatment and therefore there is a need to develop cost-effective adsorbents from alternative biomass-based low-cost raw materials to remove harmful substances from aqueous solutions. The first aim of this thesis was to determine physical and chemical properties of carbon residues from wood gasification, and fly ashes from burning processes were used as reference samples. The properties are essential to known when evaluating the potential utilisation applications for unknown carbon residue samples. Properties of carbon residue indicate that it would be suitable adsorbent due to the high carbon content but its activation or modification is needed. The second aim was to modify this industrial carbonaceous by-product by physical and chemical activation and chemical modification methods to maximise the adsorption capacity of material. Based on our results, adsorption properties can be enhanced by using zinc chloride as a chemical activating agent, carbon dioxide as a physical activating agent and ferric chloride in the chemical modification and adsorbents with specific surface areas 285, 590 and 52 m2 g-1 were produced, respectively. The third aim was to test produced adsorbents to anions removal. Chemically activated carbon residue removes phosphate well and physically activated carbon residue removes phosphates and nitrates. Chemically modified carbon residue was observed to be suitable sorbent for sulphate removal. Optimal initial pH and concentration were determined and effect of time was studied and kinetic calculations and isotherm analysis was done for studied adsorbents. / Tiivistelmä Kaasutus on tehokas tapa hyödyntää biomassaa sähkön- ja lämmöntuotannossa. Kaasutuksessa muodostuu jätteenä hiilijäännöstä, jonka hyödyntäminen on tärkeää kaasutusprosessin kustannustehokkuuden parantamiseksi. Myös nykyinen lainsäädäntö asettaa vaatimuksia jätemateriaalien hyödyntämiselle. Aktiivihiiltä on tyypillisesti käytetty mm. jäteveden sekä kaasujen puhdistukseen. Aktiivihiili on kuitenkin kallista ja sen valmistaminen on energiaa kuluttava prosessi, mikä rajoittaa sen käyttöä. Tämän vuoksi tarvitaan uutta tietoa myös kustannustehokkaampien adsorbenttien valmistamiseen soveltuvista vaihtoehtoisista biomassapohjaisista raaka-aineista. Tutkimuksen tavoitteena oli aluksi määrittää puun kaasutuksessa muodostuneen hiilijäännöksen fysikaalisia ja kemiallisia ominaisuuksia, joiden tunteminen on tärkeää arvioitaessa soveltuvia hyödyntämiskohteita kyseiselle tuntemattomalle jätemateriaalille. Referenssinäytteinä käytettiin polttolaitoksilla muodostunutta lentotuhkaa. Hiilijäännöksen ominaisuuksien perusteella se voisi olla soveltuva adsorbentti, mutta aktivointi tai modifiointi on välttämätöntä hiilijäännöksen adsorptiokapasiteetin parantamiseksi. Työn toinen tavoite oli parantaa hiilijäännöksen adsorptio-ominaisuuksia fysikaalisesti ja kemiallisesti aktivoimalla tai kemiallisesti modifioimalla. Tulosten perusteella adsorptio-ominaisuuksia voidaan parantaa parhaiten käyttämällä sinkkikloridia kemiallisessa aktivoinnissa, hiilidioksidia fysikaalisessa aktivoinnissa ja rautakloridia kemiallisessa modifioinnissa, jolloin valmistettujen adsorbenttien ominaispinta-alat olivat 285, 590 ja 52 m2 g-1. Työn kolmas tavoite oli tutkia valmistettujen adsorbenttien adsorptiokykyä anionien poistossa laboratoriomittakaavassa. Kemiallisesti aktivoitu hiilijäännös poistaa tehokkaasti fosfaattia, fysikaalisesti aktivoitu fosfaattia ja nitraattia ja kemiallisesti modifioitu hiilijäännös on hyvä sorbentti sulfaatinpoistossa. Adsorptiokokeissa määritettiin optimaalinen alku pH ja alkukonsentraatio ja lisäksi tutkittiin ajan vaikutusta adsorptioon. Tulosten perusteella tehtiin kinetiikkamallinnusta sekä isotermianalyysi.

In der vorliegenden Arbeit werden verschiedene Methoden zur Bestimmung von Sintertemperaturen für Brennstoffaschen vorgestellt und verglichen, mit dem Ziel die Agglomerationsneigung von Aschen zu charakterisieren. Es wurden Untersuchungen an drei ausgewählten Kohleaschen unter inerten, oxidierenden und reduzierenden Bedingungen durchgeführt. Die Methoden Erhitzungsmikroskopie (ASV), Hochtemperatur-Röntgendiffraktometrie (HT-RDA), Thermogravimetrische Differenz-kalorimetrie (TG-DSC), Thermodynamische Gleichgewichtsberechnungen (GGW), Elektrochemische Impedanzspektroskopie (EIS), Untersuchung der Schereigenschaften (SV) und die Bestimmung der Kaltdruckfestigkeit (KDF) wurden angewendet. Die Kombination der Untersuchungen ließ eine umfangreiche analytische Charakterisierung der Sintervorgänge zu. Unter der Berücksichtigung einer guten Vergleichbarkeit hinsichtlich der ermittelten Sintertemperaturen, stellt die EIS eine Alternative zur etablierten aber zeitaufwändigen Bestimmung der KDF dar. In Abhängigkeit von der Aschezusammensetzung, der Korngröße und der Gasatmosphäre, ist bereits ab einer Temperatur von 650 °C eine Agglomeration von Aschepartikeln möglich.

M.Sc. / The increased demand for electricity in South Africa is expected to exceed supply between 2004 and 2007. Electricity supply options in the country would be further complicated by the fact that older power stations would reach the end of their design life beyond the year 2025. In light of this and considering the long lead times required for the commissioning of new plants, new power supply options need to be proactively investigated. The environmental impacts associated with coal-fired generation of electricity have resulted in increased global concern over the past decade. To reduce these impacts, new technologies have been identified to help provide electricity from fossil fuels. The alternatives considered are gas-fired generation technologies and the Integrated Gasification Combined Cycle (IGCC). This study attempts to document and understand the environmental aspects related to gas-fired and IGCC electricity generation and evaluate their advantages in comparison to conventional pulverised coal fired power generation. The options that could be utilised to make fossil fuel electricity generation more environmentally friendly, whilst remaining economically feasible, were also evaluated. Gas-fired electricity generation is extremely successful as electricity generation systems in the world due to inherently low levels of emissions, high efficiencies, fuel flexibility and reduced demand on finite resources. Associated benefits of a Combined Cycle Gas Turbine (CCGT) are lower operating costs due to the reduced water consumption, smaller equipment size and a reduction in the wastewater that has to be treated before being returned to the environment. A CCGT plant requires less cooling water and can be located on a smaller area than a conventional Pulverised Fuel (PF) power station of the same capacity. All these factors reduce the burden on the environment. A CCGT also employs processes that utilises the energy of the fuel more efficiently, with the current efficiencies approaching 60%. Instead of simply being discharged into the atmosphere, the gas turbines’ exhaust gas heat is used to produce additional output in combination with a Heat Recovery Steam Generator (HRSG) and a steam turbine. Furthermore, as finite resources become increasingly scarce and energy has to be used as wisely as possible, generating electricity economically and in an ecologically sound manner is of the utmost importance. The clean, reliable operation of gas-fired generation systems with significantly reduced noise levels and their compact design makes their operation feasible in heavily populated areas, where electricity is needed most. At the same time, energy can be consumed in whatever form needed, i.e. as electricity, heat or steam. The dependence of the South African economy on cheap coal ensures that it will remain a vital component of future electricity generation options in the country. This dominance of coal-fired generation in the country is responsible for South Africa’s title as the largest generator of carbon dioxide (CO2) emissions on the continent and the country could possibly be requested to reduce its CO2 emissions at the next international meeting of signatories to the Kyoto Protocol. Carbon dioxide emissions can be reduced by utilising gas-fired generation technologies. However, the uncertainty and costs associated with natural gas in South Africa hampers the implementation of this technology. There are currently a number of initiatives surrounding the development of natural gas in the country, viz. the Pande and Temane projects in Mozambique and the Kudu project in Namibia, and this is likely to positively influence the choice of fuel utilised for electricity generation in the future. The economic viability of these projects would be further enhanced through the obtaining of Clean Development Mechanism (CDM) credits for greenhouse gases (GHG) emissions reduction. Alternatively, more efficient methods of generating electricity from coal must be developed and implemented. IGCC is capable of achieving this because of the high efficiencies associated with the combined cycle component of the technology. These higher efficiencies result in reduced emissions to the atmosphere for an equivalent unit of electricity generated from a PF station. An IGCC system can be successful in South Africa in that it combines the benefits of utilising gas-fired electricity generation systems whilst utilising economically feasible fuel, i.e. coal. IGCC systems can economically meet strict air pollution emission standards, produce water effluent within environmental limits, produce an environmentally benign slag, with good potential as a saleable by-product, and recover a valuable sulphur commodity by-product. Life-cycle analyses performed on IGCC power plants have identified CO2 release and natural resource depletion as their most significant positive lifecycle impacts, which testifies to the IGCC’s low pollutant releases and benign by-products. Recent studies have also shown that these plants can be built to efficiently accommodate future CO2 capture technology that could further reduce environmental impacts. The outstanding environmental performance of IGCC makes it an excellent technology for the clean production of electricity. IGCC systems also provide flexibility in the production of a wide range of products including electricity, fuels, chemicals, hydrogen, and steam, while utilizing low-cost, widely available feedstocks. Coal-based gasification systems provide an energy production alternative that is more efficient and environmentally friendly than competing coalfuelled technologies. The obstacle to the large-scale implementation of this technology in the country is the high costs associated with the technology. CDM credits and by-products sales could possible enhance the viability of implementing these technologies in South Africa.

Parmi les technologies de gazéification de la biomasse, le gazéifieur à lit fluidisé double permet la production d’un gaz de synthèse contenant du méthane. L’étude des processus physicochimiques impliqués dans le gazéifieur est rendue difficile par le fait qu’ils se produisent simultanément. Dans cette thèse, les principales réactions chimiques sont étudiées de manière découplée, indépendamment les unes des autres à l’aide de dispositifs de laboratoire originaux et dans des conditions thermiques semblables à celles du gazéifieur. Les processus intraparticulaires contrôlant la pyrolyse de la biomasse ainsi que les réactions gaz/solide (vapogazéification du charbon et craquage thermique et catalytique des vapeurs sur olivine) sont étudiées au moyen d’un four à image. Les expériences de craquage thermique homogène des vapeurs sont réalisées dans un réacteur parfaitement auto-agité par jets gazeux. Tous les produits formés par les réactions sont recueillis et analysés. Les bilans de matière bouclent de façon très satisfaisante. Le régime de chaque réaction est discuté sur la base d’une analyse de temps caractéristiques. Les paramètres cinétiques des réactions sont déterminés par modélisation des processus et optimisation à partir des résultats expérimentaux. Les mécanismes possibles de formation et de consommation du méthane sont identifiés et discutés. Le gazéifieur est modélisé sur la base d’un modèle de grains (réactions primaires de pyrolyse), des réactions secondaires, de l’hydrodynamique des phases solides et gazeuse et des transferts. La méthodologie de découplage est enfin validée par comparaison des résultats du modèle avec des mesures réalisées sur le gazéifieur de 8 MW de Güssing (Autriche) / Among the biomass gasification technologies, the dual fluidized bed gasifier may be used to produce a methane-rich syngas. Analysis of all the physicochemical phenomena involved inside the gasifier is difficult because they all occur simultaneously. In this thesis, the main chemical reactions are decoupled and studied independently one of each other at the scale of original laboratory facilities in thermal conditions close to those encountered in the gasifier. Intraparticular reactions of biomass pyrolysis and gas/solid reactions (char-steam gasification and catalytic thermal cracking of vapors on olivine) are carried out with an image furnace. Experiments related to gas-phase vapors thermal cracking are performed inside a continuous self stirred tank reactor. All the products formed by the reactions are recovered and analyzed. Mass balance closures are achieved accurately. Controlling steps of each reaction are discussed on the basis of a characteristic times analysis. Kinetic parameters are determined according to both processes modelings and optimizations from the experimental results. Different ways of possible methane formation and consumption mechanisms are identified and discussed. The gasifier is modelled by considering a single-particle model (primary pyrolysis reactions), secondary reactions, solids and gas-phase hydrodynamics and transfers. Finally, the decoupling methodology is validated from the comparison of model results with measurements performed at the 8 MW Güssing gasifier (Austria)

Depuis quelques temps, les enjeux énergétiques ne cessent d’apparaître en tête de liste des préoccupations actuelles pour l’avenir. La fin annoncée des énergies fossiles, à l’origine de 80% de celle que nous consommons aujourd’hui, s’accompagne naturellement par la recherche d’alternatives pour subvenir aux besoins futurs. L’intégration d’une dimension environnementale pour la mise en œuvre d’un développement durable met clairement en avant les atouts des énergies dites renouvelables qui concernent de nos jours moins de 15% de la production mondiale. Le travail proposé ici s’inscrit dans ce cadre de recherche et de proposition de sources d’énergies primaires renouvelables avec l’étude de valorisation de déchets contenant de la biomasse et plus particulièrement du cas du revêtement de sol stratifié. Parmi les diverses voies de valorisation actuelles, l’incinération avec l’ensemble des autres déchets reste le plus usité. L’inconvénient majeur réside dans la nécessité de traitement des fumées qui s’avère relativement coûteux. Il semblerait donc judicieux d’envisager une autre issue de valorisation. Le procédé proposé fait apparaître les trois étapes suivantes : une étape de prétraitement par pyrolyse à basse température (275°C) assurant une séparation des éléments azotés (précurseurs susceptibles de conduire à la formation de polluants) en altérant au minimum le matériau en vue d’une récupération maximale d’énergie lors de l’étape suivante ; une étape de valorisation énergétique, qui constitue le centre du procédé, par une pyrolyse à haute température (1000°C). L’énergie est obtenue par l’intermédiaire du gaz de synthèse ; et une étape de valorisation matière sous deux aspects avec l’obtention de produits à valeur ajoutée (panneaux de particules et charbons actifs) dont l’entrée dans le bilan économique global d’une installation industrielle pourrait s’avérer intéressante / Since a few years, energy challenges are appearing at the top of the list of the current concerns for the future. The forecasted end of fossil fuels, at the origin of 80% of currently consumed energy, is obviously accompanied by research about alternatives to provide for the future needs. The integration of an environmental care concerning the implementation of a sustainable development puts clearly ahead the assets of renewable energies which constitutes nowadays less than 15% of the worldwide production. Work suggested here deals with this scope of research and proposal for renewable primary energy sources with the recovery study of waste containing biomass and more precisely the case of laminated flooring. Among the various current recovering ways, incineration with the whole waste remains the most used one. The main drawback deals with the need for smoke treatment, the cost of which can be really high. It would thus seem to be judicious to look for another recovering issue. The suggested process is divided in the three following steps: - A pretreatment step through low temperature pyrolysis (275°C) making it possible a nitrogenous components separation of the elements (precursor able to form pollutants species) in deteriorating the fuel the less as possible to provide a maximum energy recovery in the following stage.- An energy recovery step, which constitutes the main goal of the process, through a high temperature pyrolysis (1000°C). Energy is recovered via syngas.- A material recovery step through two aspects in order to produce added-value material (particle boards and activated carbon), the consideration of which in the global economic assessment of an industrial installation could be interesting

Renewability and the carbonaceous basis of biomass provide potential for both energy and chemical production in biorefineries in a fashion similar to crude oil refineries. Biorefineries are envisaged as having a key role in the transition to a more sustainable industry, especially as a means to mitigate greenhouse gas (GHG) emissions. A biorefinery is a concept for the flexible, efficient, cost-effective and sustainable conversion of biomass through a combination of process technologies into multiple products. This implies that biorefineries must be integrated through designs that exploit the interactions between material and energy streams. The wide range of possibilities for biomass feedstock, processes and products poses a challenge to biorefinery design. Integrating biorefineries within evolving economic and environmental policy contexts requires careful analysis of the configurations to be deployed from early in the design stage. This research therefore focuses on the application and development of methodologies for biorefinery design encompassing process integration tools, economic and environmental sustainability analyses together. The research is presented in the form of papers published or submitted to relevant peer-reviewed journals, with a preamble for each paper and a final synthesis of the work as a whole. In a first stage, mass pinch analysis was adapted into a method for integration ofbiorefineries producing bioethanol as a final product and also utilising bioethanol asa working fluid within the biorefinery. The tool allows targeting minimum bioethanol utilisation and assessing network modifications to diminish revenue losses. This new application could stimulate the emergence of similar approaches for the design of integrated biorefineries. The thesis then moves to combine feedstock production models, process simulations in Aspen Plus® and process integration with LCA, to improve energy efficiency and reduce GHG emissions of biorefineries. This work, presented via two publications covering wheat to bioethanol and Jatropha to biodiesel or green diesel, provided evidence of the benefits of biorefinery integrationfor energy saving and climate change adaptation. The multilevel modelling approach is then further integrated into a methodologydeveloped for the combined evaluation of the economic potential and GHG emissions saving of a biorefinery from the marginal performances of biorefineryproducts. The tool allows assessing process integration pathways and targeting forpolicy compliance. The tool is presented via two further publications, the first drawing analogies between value analysis and environmental impact analysis inorder to create the combined Economic Value and Environmental Impact (EVEI)analysis methodology, the second extending this to demonstrate how the tool canguide judicious movement of environmental burdens to meet policy targets. The research embodied in this thesis forms a systematic basis for the analysis andgeneration of biorefinery process designs for enhanced sustainability. The toolspresented will facilitate both the implementation of integrated biorefinery designsand the cultivation of a community of biorefinery engineers for whom suchintegrated thinking is their distinctive and defining attribute.

Fossil fuels constitute a significant fraction of the world’s energy demand. The burning of fossil fuels emits huge amounts of carbon dioxide into the atmosphere. Therefore, the limited availability of fossil fuel resources and the environmental impact of their use require a change to alternative energy sources or carriers (such as hydrogen) in the foreseeable future. The development of methods to mitigate carbon dioxide emission into the atmosphere is equally important. Hence, extensive research has been carried out on the development of cost-effective technologies for carbon dioxide capture and techniques to establish hydrogen economy. Hydrogen is a clean energy fuel with a very high specific energy content of about 120MJ/kg and an energy density of 10Wh/kg. However, its potential is limited by the lack of environment-friendly production methods and a suitable storage medium. Conventional hydrogen production methods such as Steam-methane-reformation and Coal-gasification were modified by the inclusion of NaOH. The modified methods are thermodynamically more favorable and can be regarded as near-zero emission production routes. Further, suitable catalysts were employed to accelerate the proposed NaOH-assisted reactions and a relation between reaction yield and catalyst size has been established. A 1:1:1 molar mixture of LiAlH4, NaNH2 and MgH2 were investigated as a potential hydrogen storage medium. The hydrogen desorption mechanism was explored using in-situ XRD and Raman Spectroscopy. Mesoporous metal oxides were assessed for CO2 capture at both power and non-power sectors. A 96.96% of mesoporous MgO (325 mesh size, surface area = 95.08 ± 1.5 m2/g) was converted to MgCO3 at 350°C and 10 bars CO2. But the absorption capacity of 1h ball milled zinc oxide was low, 0.198 gCO2 /gZnO at 75°C and 10 bars CO2. Interestingly, 57% mass conversion of Fe and Fe3O4 mixture to FeCO3 was observed at 200°C and 10 bars CO2. MgO, ZnO and Fe3O4 could be completely regenerated at 550°C, 250°C and 350°C respectively. Furthermore, the possible retrofit of MgO and a mixture of Fe and Fe3O4 to a 300 MWe coal-fired power plant and iron making industry were also evaluated.