In this dissertation we address three different sustainability concepts: [1] modeling of biodiesel production via heterogeneous catalysis, [2] life cycle analysis for pyrolysis of switchgrass for using in power plant, and [3] modeling of pyrolysis of biomass. Thus we deal with Specific Aim 1, 2 and 3. In Specific Aim 1, the models for esterification in biodiesel production via heterogeneous catalysis were developed. The models of the reaction over the catalysts were developed in two parts. First, a kinetic study was performed using a deterministic model to develop a suitable kinetic expression; the related parameters were subsequently estimated by numerical techniques. Second, a stochastic model was developed to further confirm the nature of the reaction at the molecular level. The deterministic and stochastic models were in good agreement. In Specific Aim 2, life cycle analysis and life cycle cost for pyrolysis of switchgrass for using in power plant model were developed. The greenhouse gas (GHG) emission for power generation was investigated through life cycle assessment. The process consists of cultivation, harvesting, transportation, storage, pyrolysis, transportation and power generation. Here pyrolysis oil is converted to electric power through co- combustion in conventional fossil fuel power plants. The conventional power plants which are considered in this work are diesel engine power plant, natural gas turbine power plant, coal-fired steam-cycle power plant and oil-fired steam-cycle power plant. Several scenarios are conducted to determine the effect of selected design variables on the production of pyrolysis oil and type of conventional power plants. In Specific Aim 3, pyrolysis of biomass models were developed. Since modeling of pyrolysis of biomass is complex and challenging because of short reaction times, temperatures as high as a thousand degrees Celsius, and biomass of varying or unknown chemical compositions. As such a deterministic model is not capable of representing the pyrolysis reaction system. We propose a new kinetic reaction model, which would account for significant uncertainty. Specifically we have employed fuzzy modeling using the adaptive neuro-fuzzy inference system (ANFIS) in order to describe the pyrolysis of biomass. The resulting model is in better agreement with experimental data than known deterministic models. / Ph. D.

Biomass fast pyrolysis liquid (bio-oil) is a cellulose based alternative fuel with the potential to displace fossil fuels in stationary heat and power applications. To better understand the combustion behavior and emissions of bio-oil, a 10 kW spray burner was designed and constructed. The effect of swirl, atomization quality, ignition source (pilot) energy, air/fuel preheat and equivalence ratio on the stability and emissions of bio-oil spray flames was investigated. A blend of 80% pyrolysis liquid and 20% ethanol by volume was used during the tests and the results were compared to burner operation with diesel. It is important to have good atomization, thorough mixing and high swirl in order to stabilize ignition, promote the burnout of bio-oil and decrease CO, hydrocarbon and particulate matter emissions. The total amount of primary air and atomizing air that can be used to improve turbulence, mixing, droplet burnout and overall combustion quality is limited by the distillable fraction and narrow lean blow-out limit associated with pyrolysis liquid. Air and fuel preheat are important for reducing hydrocarbon and CO emissions, although subsequent fuel boiling should be avoided in order to maintain flame stability. The NOx produced in bio-oil flames is dominated by the conversion of fuel bound nitrogen. The particulate matter collected during bio-oil combustion is composed of both carbonaceous cenosphere residues and ash. Under good burning conditions, the majority consists of ash. Pilot flame energy and air/fuel preheat have a weak effect on the total particulate matter in the exhaust. Generally, these results suggest that available burner parameters can be adjusted in order to achieve low hydrocarbon, CO and carbonaceous particulate matter emissions when using pyrolysis liquid. Total particulates can be further mitigated by reducing the inherent ash content in bio-oil. Comparative burner tests with diesel reveal much lower emissions for this fuel at most of the operating points considered. This is due to the fully distillable nature, better atomization and improved spray ignition characteristics associated with diesel. Because of its superior volatility, diesel can also operate over a much wider range of primary air and atomizing air flow rates compared to bio-oil.

Biomass fast pyrolysis liquid (bio-oil) is a cellulose based alternative fuel with the potential to displace fossil fuels in stationary heat and power applications. To better understand the combustion behavior and emissions of bio-oil, a 10 kW spray burner was designed and constructed. The effect of swirl, atomization quality, ignition source (pilot) energy, air/fuel preheat and equivalence ratio on the stability and emissions of bio-oil spray flames was investigated. A blend of 80% pyrolysis liquid and 20% ethanol by volume was used during the tests and the results were compared to burner operation with diesel. It is important to have good atomization, thorough mixing and high swirl in order to stabilize ignition, promote the burnout of bio-oil and decrease CO, hydrocarbon and particulate matter emissions. The total amount of primary air and atomizing air that can be used to improve turbulence, mixing, droplet burnout and overall combustion quality is limited by the distillable fraction and narrow lean blow-out limit associated with pyrolysis liquid. Air and fuel preheat are important for reducing hydrocarbon and CO emissions, although subsequent fuel boiling should be avoided in order to maintain flame stability. The NOx produced in bio-oil flames is dominated by the conversion of fuel bound nitrogen. The particulate matter collected during bio-oil combustion is composed of both carbonaceous cenosphere residues and ash. Under good burning conditions, the majority consists of ash. Pilot flame energy and air/fuel preheat have a weak effect on the total particulate matter in the exhaust. Generally, these results suggest that available burner parameters can be adjusted in order to achieve low hydrocarbon, CO and carbonaceous particulate matter emissions when using pyrolysis liquid. Total particulates can be further mitigated by reducing the inherent ash content in bio-oil. Comparative burner tests with diesel reveal much lower emissions for this fuel at most of the operating points considered. This is due to the fully distillable nature, better atomization and improved spray ignition characteristics associated with diesel. Because of its superior volatility, diesel can also operate over a much wider range of primary air and atomizing air flow rates compared to bio-oil.

The last couple of decades have seen entrained-flow gasification of black liquor (BL) undergo an incremental process of technical development as an alternative to combustion in a recovery boiler. The ability of the technology to combine chemical recovery with the production of clean syngas renders it a promising candidate for the transformation of chemical pulp mills into integrated forest biorefineries. However, techno-economic assessments have shown that blending BL with the more easily transportable pyrolysis oil (PO) can not only increase the system efficiency for methanol production but remove a significant roadblock to development by partially decoupling production capacity from limitations on black liquor availability. The verification and study of catalytic co-gasification in an industrially-relative scale can yield both scientifically interesting and practically useful results, yet it is a costly and time-consuming enterprise. The expense and time involved can be significantly reduced by performing thermodynamic equilibrium calculations using a model that has been validated with relevant experimental data. The main objective of this thesis was to study, understand, quantify and compare the gasification behaviour and process performance of black liquor and pyrolysis oil blends in pilot-scale. A secondary objective of this work was to demonstrate and assess the usefulness and accuracy of unconstrained thermodynamic equilibrium modelling as a tool for studying and predicting the characteristics of alkali-impregnated biomass entrained-flow gasification. The co-gasification of BL/PO blends was studied at the 3 MWth LTU Green Fuels pilot plant in a series of experimental studies between June 2015 and April 2016. The results of the studies showed that the blending of black liquor with the more energy rich pyrolysis oil increased the energetic efficiency of the BLG process without adversely affecting carbon conversion. The effect of blend ratio and reactor temperature on the gasification performance of PO and BL blends with up to 20 wt% PO was studied in order to assess the impact of alkali-dilution in fuel on the conversion characteristics. In addition to unblended BL, three blends with PO/BL ratios of 10/90, 15/85 and 20/80 wt% were gasified at a constant load of 2.75 MWth. The decrease in fuel inorganic content with increasing PO fraction resulted in more dilute green liquor (GL) and a greater portion of the feedstock carbon ended up in syngas as CO. As a consequence, the cold gas efficiency increased by about 5%-units. Carbon conversion was in the range 98.8-99.5% and did not vary systematically with either fuel composition or temperature. The validation of thermodynamic equilibrium simulation of black liquor and pyrolysis co-gasifications with experimental data revealed the need to be mindful of errors and uncertainities in fuel composition that can influence predictions of equilibrium temperature. However, provided due care is to taken to ensure the use of accurate fuel composition data, unconstrained TEMs can serve as a robust and useful tool for simulating catalytic entrained-flow gasification of biomass-based feedstocks. / LTU Biosyngas (Catalytic Gasification)

Actuellement la production d’huile pyrolytique (ou bio-huile) est destinée à en faire un carburant pour les moyens de transport. Cependant, le liquide issu de la pyrolyse est de piètre qualité, il est nécessaire de faire une opération d’hydrodéoxygénation (HDO), très coûteuse et énergivore, pour aboutir à un produit ayant les spécificités d’un carburant. Une des idées proposées, plus économique, consiste à faire de la bio-huile une source de biosyngas (CO+H2) ou biohydrogène renouvelables via du vaporeformage (VR). Ce projet de maitrise étudie le reformage à la vapeur d’eau de deux bio-huiles (MemU et WOU) sans apport externe de vapeur sur un nouveau catalyseur à base de nickel, Ni-UGSO, développé par le GRTP-C à partir du résidu minier UGSO. Les expériences de reformage ont été réalisées à pression atmosphérique, dans un réacteur différentiel et pour une durée de 500 min en faisant varier la température (750-850 °C) et la vélocité spatiale (WHSV= 1.7-7.1 g/gcat/h) en plus d’un test longue durée à 105h. Des tests supplémentaires ont été réalisés aussi avec un catalyseur commercial à titre de comparaison en plus d’un test de régénérabilité. La caractérisation du catalyseur s’est faite par DRX, MEB-FEG, BET et TPR. Les résultats des tests de VR de l’huile MemU entre 750 et 850 °C à WHSV ~1.8 g/gcat/h montrent une bonne production de biosyngas avec une concentration entre 90-95% et une sélectivité en H2 entre 80-95%. Le VR de l’huile WOU dans les mêmes conditions a donné moins de biosyngas et de H2 en raison de la teneur élevée en eau de l’huile. Le catalyseur est resté actif pendant toute la durée des tests, la DRX et la MEB ne montrent aucune trace de carbone. Cependant à WHSV > 6 g/gcat/h du carbone filamenteux sur le catalyseur a été observé par MEB après le VR de l’huile MemU mais pas après le VR de l’huile WOU. La DRX a permis aussi de montrer qu’après le VR des huiles, les oxydes de Fe et Ni qui constituent le catalyseur se réduisent et se combinent pour donner du Ni métallique et des alliages Ni-Fe. Le test BET indique que le catalyseur a une surface spécifique, après activation, de 10 m2/g. La TPR montre qu’il y a plus d’espèces oxydées sur le Ni-UGSO après le VR de la bio-huile WOU qu’après le VR de la bio-huile MemU, d’où les faibles rendements en H2/biosyngas. Les tests de VR réalisés avec le catalyseur commercial montrent des résultats similaires que ceux réalisés avec Ni-UGSO à faible WHSV. Cependant à WHSV élevée le catalyseur commercial a été plus résiliant et plus performant du fait de sa grande surface spécifique. Le test de régénérabilité montre que Ni-UGSO ne peut que partiellement être régénéré et sa structure initiale n’est pas retrouvée Les résultats positifs confirment que la production de biosyngas/biohydrogène par VR de bio-huiles est viable techniquement dans une bioraffinerie. Le procédé est plus économique que l’HDO. De plus, l’huile pyrolytique se trouve être une bonne matière première pour le reformage car on a un bon rendement en biosyngas (ou H2). Le catalyseur Ni-UGSO développé par le GRTP-C a montré des performances similaires que celles de catalyseurs actuellement sur le marché mais nécessite d’être encore optimisé. / Abstract : Currently the production of pyrolysis oil (or bio-oil) is intended to be transformed to transportation fuel. However, the produced liquid is of bad quality and it needs a hydrodeoxygenation (HDO) process which is very expensive and lot of energy is consumed to obtain a final product with the right fuel specifications. One of the ideas proposed, more economical, consists on producing renewable biosyngas (CO+H2) or biohydrogen from biooil by steam reforming (SR). This master project study the steam reforming of two bio-oils (MemU and WOU) without external steam addition over a new nickel based catalyst, Ni-UGSO, developed by the GRTP-C from the mining residue UGSO. The reforming tests were carried out at atmospheric pressure in a differential reactor during 500 min varying the temperature (750- 850 °C) and the weigh hourly space velocity (WHSV= 1.7-7.1 g/gcat/h), a long term test of 105h was also performed. In addition, Supplementary tests were done with a commercial catalyst in order of comparison plus one regenerability test. The catalyst characterization was done by XRD, FEG-SEM, BET and TPR. Test results of bio-oil MemU SR at 750-850 °C and WHSV ~ 1.8 g/gcat/h show a good production of biosyngas with a concentration range of 90-95% and a H2 selectivity of 80- 95%. The SR of bio-oil WOU in the same conditions resulted in less biosyngas and H2 produced because of high water content in the bio-oil. The catalyst was active for the whole duration of tests, XRD and SEM indicate that no carbon deposit was formed. However at WHSV > 6 g/gcat/h filamentous carbon was observed on the catalyst by SEM after the SR of bio-oil MemU but not after the SR of bio-oil WOU. The XRD showed also that after biooils SR Fe and Ni oxides that constitute the catalyst are reduced to metallic Ni and Ni-Fe alloys. BET test indicate that after activation the catalyst has a specific area of 10 m2 /g. TPR shows that more oxidized species are present in Ni-UGSO after bio-oil WOU SR than after bio-oil MemU SR which explains low H2/biosyngas yield. The tests of SR performed with the commercial catalyst show similar results as those performed with Ni-UGSO at low WHSV. However, at high WHSV the commercial catalyst was more resilient and better due to its high specific area. Regenerability test shows that NiUGSO is partially regenerated but its initial structure is not recovered. The positive results confirm that the production of biosyngas/biohydrogen from SR of biooils is technically viable for a biorefinery. The process is economically better than the HDO. The pyrolysis oil is a good feedstock for the reforming, we obtain an appreciable yield of biosyngas (or H2). The catalyst Ni-UGSO developed by the GRTP-C exhibits similar performances than commercial catalysts actually available in the market but needs more optimisation.

The diploma thesis is focused on the energy utilization of sewage sludge before and after microwave pyrolysis process. The first part of the thesis deals with sludge management, treatment of sludge and its subsequent use or disposal. In the second part of the thesis prepared and modified samples of sludge from WWTP 1 and WWTP 2 are subjected to microwave pyrolysis process. Subsequently, samples are taken for analyzes to determine the total organic carbon, the specific surface area, the heavy metal content and the calorific values. The resulting data was processed in Microsoft Office Excel and presented at work. At the end of the thesis two case studies are then proposed for a specific design of the conceptual location of microwave pyrolysis for the sludge drying process and the drying process of the sewage sludge in the direct combustion boiler room.

La pyrolyse rapide est un procédé thermochimique permettant la transformation de la biomasse lignocellulosique en liquide. Cette bio-huile n'est pas utilisable directement de par son instabilité thermique, sa faible capacité calorifique et son immiscibilité avec les hydrocarbures due à une teneur élevée en composés organiques oxygénés. Un procédé de raffinage prometteur est l'hydroconversion catalytique permettant la conversion de ces composés et le retrait significatif de l'oxygène. Cependant, des réactions compétitives telles que la condensation ou l'oligomérisation sont observées. Compte tenu de la complexité des bio-huiles, des molécules modèles sont étudiées pour mieux comprendre ces réactions. Les molécules choisies pour cette thèse sont le D-glucose, le furfural, l'acide acétique et le guaiacol dans l'eau. Les tests expérimentaux ont été effectués dans un réacteur fermé isotherme dont la charge est constituée de 150 g de mélanges et 15 g de catalyseur frais NiMo/?-Al2O3. La température d'étude varie entre 200°C et 300°C jusqu'à 3 h de réaction. Une pression d'H2 a été maintenue constante afin de rejoindre une pression totale de 13 MPa. Les réactions de désoxygénation et compétitives ont été observées à travers la complexification croissante de la charge assistée par une stratégie analytique multi-technique des effluents liquides et solides. L'hydroconversion catalytique du furfural et du D-glucose mène vers une grande variété de composés provenant de réactions d'hydrogénation, de déshydratation, de décarbonylation et de décarboxylation ou de retro-aldolisation. Une faible quantité de produits a été détectée par GC et LC mais, en parallèle, l'analyse SEC a mis en évidence la formation de macromolécules. En phase aqueuse, ces macromolécules précipitent au-delà de 700 g/mol PS équivalent. Les analyses 13C RMN de résidus solides formés par le D-glucose ont montré la présence de liaisons furaniques et aromatiques produites en phase liquide par des réactions de déshydratation. Le mélange à 4 composés a mis en évidence le rôle du guaiacol comme limitant de résidus en solubilisant et en réagissant avec ces macromolécules pour en former des structures dépassant 5000 g/mol PS équivalent. Les mêmes conditions opératoires ont été adoptées pour l'étude d'une bio-huiles de pyrolyse de résidus forestiers dont la conversion a montré des similitudes dans la formations et dans la structure des macromolécules / One of the thermochemical liquefaction processes used to transform lignocellulosic biomass into liquid is flash pyrolysis. The obtained bio-oils have limited end-user application due to their thermal instability, low heat capacity and immiscibility with hydrocarbons resulting from a high oxygen content. A promising upgrading process is the catalytic hydroconversion that performs a significant oxygen removal. However competitive reactions such as condensation or oligomerization can be observed. Regarding the bio-oil complexity, model molecules lead to a better understanding of those reaction. Investigated model compounds in this PhD. were D-glucose, furfural, acetic acid and guaiacol in water. Experimental tests were carried out in an isothermal 500 ml stirred batch reactor subsequently feed by 150 g mixture and 15 g of fresh reduced NiMo/?-Al2O3 catalyst. The reaction temperature varied from 200°C to 300°C during a reaction time up to 3 h. A H2 atmosphere was set to maintain a constant total pressure of 13 MPa during the run. Deoxygenation and side-reactions were observed through a gradual reactant addition in the studied mixtures using an original analytical strategy of liquid and solid effluents based on various technique. Furfural and D-glucose single hydroconversion lead to a wide range of by-products mainly issued from hydrogenation, dehydration, decarbonylation/decarboxylation or aldol reactions. A low quantity of carbon quantified by GC and LC in the liquid phase was observed during the conversion corresponding to the formation of soluble macromolecules which were detected by the size-exclusion chromatography (SEC) analysis. In a water medium, those products were prone to precipitate from 700 g/mol PS equivalent. 13C NMR of D-glucose’ solid residues revealed furanic and aromatic boundaries. Such compounds were likely formed through dehydration reactions. Regarding the final 4-component mixture, the presence of guaiacol decreased the solid production by solubilizing and/or reacting with macromolecules arising from D-glucose and furfural leading to the production of larger macromolecules (up to 5.000 g/mol) in the liquid phase. The same operational conditions were used with bio-oil to observe and characterize similar macromolecules formation and structures

När befolkningsmängden ökar och teknisk och ekonomisk utveckling sker så påverkas även energianvändningen. Detta ställer krav på att energitillförseln är säker, stabil och hållbar. I dag är det fossila bränslen som dominerar globalt sett vilket får konsekvenser för den miljö vi lever i, och dessutom är det en ändlig, ohållbar resurs. Därför behöver dessa ersättas av hållbara alternativa energikällor, vilket också är centralt för miljömål i både Sverige och i den Europeiska Unionen. Förhoppningar finns om att processer som omvandlar lignocellulosa till fasta, flytande och gasformiga drivmedel och bränslen kan bidra till omställningen från fossilt till förnybart. I detta examensarbete som utförts i samarbete med KTH och IVL Svenska Miljöinstitutet har främst en av dessa omvandlingsprocesser undersökts närmare – pyrolys. Pyrolys är en termisk process som omvandlar lignocellulosa under temperaturer mellan cirka 300-650 °C under syrefria förhållanden. Tre faser kan erhållas. En gasfas som kan kondenseras till pyrolysolja, en fast fas som benämns biokol eller kol (beroende på slutanvändning) och en okondenserbar gasfas. Utbytet av produkter och kvalitet på dessa styrs främst av: typ av råvara, typ av reaktor och av vilka processförhållanden som råder. En undersökning av olika pyrolysprocessers status på marknaden har gjorts. Graden av kommersialisering och status i nuläget och hur framtiden kan se ut för både tekniken och produkterna har uppskattats genom litteraturstudier, internetsökningar och intervjuer med utvalda företag och personer med kunskaper inom pyrolys. Rapporten visar att pyrolys inte ännu är en helt kommersiell process, men att den har möjlighet att bli det med rätt förutsättningar. Det är svårt att säga när det sker, då det förutom fortsatt teknisk utveckling, ökad kunskap kring pyrolysprocessen och resultat av demonstrationer beror på olika externa faktorer. Yttre faktorer för kommersialisering av pyrolys i Sverige har identifierats som ökad säkerhet kring politiska styrmedel och beslut kring långsiktiga sådana (osäkerhet och kortsiktiga beslut skrämmer bort investerare), vikten av att etablera en värdekedja för att säkra investeringen, och priser på fossila drivmedel och biomassa som råvara. Processer för produktion av biokol verkar dock ha hunnit längre än de för pyrolysolja och är i ett tidigt stadium av kommersialisering.  Den enda tillämpningen som är fullt kommersiell idag är produktion av träkol och för detta tillämpas ofta traditionella satsvisa processer. Många möjliga användningsområden för produkterna finns där de har potential att reducera koldioxidutsläpp och bidra till en mer hållbar framtid. Standardisering och certifiering av produkter är då viktigt, samt demonstration av användning. Stabilisering och vidare förädling av pyrolysoljan är en annan viktig faktor för kommersialisering. Ännu verkar processer för katalytisk uppgradering inte vara tillräckligt tekniskt eller ekonomiskt utvecklade för att ge en konkurrenskraftig produkt, men forskning pågår kring detta. Integrering av processen ser ut att kunna öka energieffektiviteten, samt bidra till minskade produktionskostnader. / The population growth as well as a rapid technical and economic development globally affects the energy consumption. This requires a secure, stable and sustainable supply of energy. Today fossil fuels dominate globally and this results in environmental problems. Fossil fuels are also a finite, unsustainable resource. Thus, there is a need to replace fossil fuels with sustainable alternative sources of energy. This is also central for environmental goals both in Sweden and in the European Union. There are expectations that processes for the conversion of lignocellulosic biomass to solid, liquid and gaseous fuels can contribute to a transition from fossil to renewable fuels. In this thesis, carried out in collaboration between KTH and IVL Swedish Environmental Research Institute, one of the conversion processes is investigated in detail – pyrolysis. Pyrolysis is a thermal process that converts lignocellulose under anaerobic conditions at temperatures between about 300-650°C. Three phases can be obtained as products. A volatile which can be condensed into pyrolysis oil, a solid which may be termed biochar or charcoal depending on the end use, and a gas phase. The yield and the quality of the products is dependent upon the type of raw material, the type of reactor and the process conditions. An examination of the status of different pyrolysis processes on or on the way to the market has been made. The current degree of commercialization and what the future may look like for both the technology and the products have been assessed through literature studies, internet searches, and interviews with selected companies and individuals with expertise in pyrolysis.   This report reveals that continuous pyrolysis is not yet a fully commercial process, but that it has the opportunity to reach commercialization during the right conditions. It is difficult to say when it occurs, due to various external factors, continued technical development, increased knowledge of the pyrolysis process and results of the current demonstrations. In this report, several critical factors for the commercialization of pyrolysis in Sweden have been identified, e.g. increased stability for policy instruments and that will limit the risk for investments (uncertainty and short-term decisions frightens investors) and the establishment of a value chain for the products, i.e. a stable market. Prices on fossil fuels and biomass feedstock are also important factors. Processes for the production of biochar is in the early stages of commercialization, and seem to have reached further in their development than processes for pyrolysis oil. The only fully commercial application of pyrolysis today is the production of charcoal that commonly is performed in traditional batch-wise processes. There are many possible uses for the products in which they have the potential to reduce carbon emissions and contribute to a more sustainable future. Standardization and certification of products is important, and demonstration of the use. Stabilization and further upgrading of pyrolysis oil is another important factor for commercialization. It seems like processes for catalytic upgrading are not yet sufficiently technically or financially developed to be able to provide a competitive product. Research and development in this area are ongoing. Integration of the process with incumbent industrial processes seems to be able to offer increased energy efficiency and reduced production costs.

The main theme of this thesis is available and potential gaseous and liquid alternative biofuels made from biomass and waste. The thesis deals with their detailed description and comparison. The first part covers the basic distribution of biofuels and alternative fuels made from waste. The main part focuses then on the fuels themselves, their properties, production, use and environmental impact. Furthermore, thesis describes legislative issues and fuels are compared from different perspectives. Practical part includes testing of combustion of liquid fuels taken from waste sources. In the next chapters there is executed overview of basic atomization method of liquid fuels and a plan and running of the testing processed. Evaluation of results is based on point of view of suitability for use, the quality of combustion and emission limits.

Les produits issus de la biomasse végétale connaissent depuis quelques années un succès grandissant dans de nombreuses industries (aromathérapie, cosmétique, parfums, etc.). L’objectif de notre étude était, d’une part de contribuer au développement des méthodes d’identification et de quantification des constituants des mélanges naturels par RMN 13C et RMN 1H (par exemple le squalène dans l’huile d’olive), et d’autre part, de contribuer à la caractérisation chimique de deux conifères introduits en Corse, le pin d’Alep (huile essentielle) et le cèdre de l’Atlas (huile essentielle, huile pyrolytique et résine).La première partie concerne la quantification du squalène présent dans l’huile d’olive. En effet, ce triterpène linéaire participe à la stabilité oxydative de l’huile d’olive et joue un rôle important dans la réduction des risques de certains cancers. Il s’agissait de mettre au point un protocole expérimental basé sur la RMN 1H ou 13C en utilisant un appareil de routine (9,4 Tesla). La quantification par RMN 13C s’est avérée fiable et elle a été appliquée à la quantification du squalène dans 25 échantillons d’huile d’olive de Corse.La seconde partie de nos travaux concerne la caractérisation chimique de l’huile essentielle de pin d’Alep introduit dans trois stations de Corse (Capo di Feno, Saleccia et Tre Padule de Suartone). L’analyse détaillée de l’huile essentielle de cônes, par combinaison des techniques chromatographiques et spectroscopiques, a permis d’identifier 48 composés. La composition chimique est largement dominée par les monoterpènes (Alpha-pinène et myrcène) et un sesquiterpène oléfinique ((E)-Béta-caryophyllène). La RMN 13C a permis d’identifier divers diterpènes, dont le 8,12-époxy-14-labdèn-13-ol. Ce composé est décrit pour la première fois dans l’huile essentielle de pin d’Alep. L’analyse de 15 échantillons d’huile essentielle de cônes a mis en évidence trois types de compositions : Alpha-pinène ; myrcène ; Alpha-pinène/myrcène. Enfin, l’analyse de 47 échantillons d’huile essentielle d’aiguilles, associée à un traitement statistique des données (ACP, AFD), a permis de mettre en évidence une variabilité chimique intraspécifique. Ainsi, les échantillons se répartissent en trois groupes selon leur teneur en (E)-Béta-caryophyllène (groupe I), en E-Béta-caryophyllène/Alpha-pinène/myrcène (groupe II) et en myrcène (groupe III).La dernière partie a été consacrée à l’étude de Cedrus atlantica. L’analyse détaillée d’une huile essentielle commerciale (du Maroc) a permis d’identifier 20 constituants, les composés majoritaires sont les Alpha-, Béta- et Gamma-himachalène. Par ailleurs, 7 composés absents de notre bibliothèque de données spectrales ont été identifiés par RMN 13C. Les compositions chimiques des huiles pyrolytiques artisanales du Maroc sont également dominées par les himachalènes et la (E)-Alpha-atlantone. Enfin, nous avons réalisé l’analyse qualitative et quantitative par RMN 13C, sans séparation préalable, de 28 échantillons de résine de C. atlantica récoltés dans les 5 forêts de Corse référencées par l’ONF (Bavella, Bonifato, Ospedale, Pineta et Vizzavona). A côté des acides résiniques, nous avons également identifié 3 lignanes (pinorésinol, laricirésinol et 9-acétate de laricirésinol). Pour l’ensemble de ces composés, nous avons mis en évidence trois types chimiques. Enfin, nous avons mis au point et validé un protocole expérimental de quantification des lignanes par RMN 1H. / Natural products isolated from plants acquired, in recent years, a growing success in many industries (aromatherapy, cosmetic, perfumes). The objective of our study was to contribute, on the one hand, to the development of methods involving 13C and 1H NMR for the identification and quantification of the components of natural mixtures, and on the other hand, to the chemical characterization of two conifers brought to Corsica, Aleppo pine (essential oil) and atlas cedar (essential oil, pyrolysis oil and resins).The first part concerned the quantification of squalene present in olive oil. Indeed, linear triterpene participated in the oxidative stability of olive oil and play an important role by decreasing some kind of cancers risks. It’s deal with to elaborate an experimental part based on NMR 1H and 13C by using routine apparatus (9.4 Tesla). Quantification by NMR 13C is reliable and have been applied to squalene quantification in 25 samples of Corsican olive oil.The second part of our work concerned the chemical characterization of the essential oil of Aleppo pine brought to Corsica in three different stations (Capo di Feno, Saleccia and Tre Padule de Suartone). A detailed analysis of cone essential oil, using the combination of chromatographic and spectroscopic techniques, leads to the identification of 48 compounds. Chemical composition is extensively dominated by monoterpens (Alpha-pinene and myrcene) and one olefinic sesquiterpen ((E)-Béta-caryophyllene). 13C NMR allowed to the identification of various diterpens, particularly the 8,12-epoxy-14-labden-13-ol. This compound is described for the first time in aleppo pine essential oil. Fifteen samples of cone essential oil were analysed allowing differentiating three kinds of compositions: Alpha-pinene; myrcene; Alpha-pinene/myrcene. Finally, analysis of 47 samples of needles essential oil, associated with statistical treatment of the results (PCA and PFA), suggested the occurrence of an intraspecific chemical variability. Samples are divided into three groups, based on their high contents in (E)-Béta-caryophyllene (groupe I), in (E)-Béta-caryophyllene/Alpha-pinene/myrcene (groupe II) and in myrcene (groupe III).The last part concerned the study of Cedrus atlantica. A detailed analysis of commercial essential oil leads to the identification of 20 constituents. Main compounds are Alpha-, Béta- and Gamma-himachalene. Moreover, seven compounds, not yet referenced in our home-made NMR spectral data library, were identified by NMR 13C. Chemical compositions of handwork pyrolysis oils from Morocco were also dominated by the himachalene’s and (E)--atlantone. Qualitative and quantitative analysis of 28 samples of Cedrus atlantica resins, obtained from the five Corsican forests referenced by the Office National des Forêts of Corsica (Bavella, Bonifato, Ospedale, Pineta and Vizzavona) have been done, without any step of chromatography. Beside resinic acids, we have been identified three lignans (pinoresinol, lariciresinol and lariciresinol-9-acetate). Qualitative and quantitative analysis of these compounds, leads to the occurrence of three types of chemical composition. Finally, we have developed and validated a method for quantification of lignans by 1H NMR.