Les procédés thermochimiques solaires étudiés concernent la conversion de charges hydrocarbonées solides ou gazeuses en syngas, ainsi que la réduction d’oxydes en métaux en utilisant l’énergie solaire concentrée pour effectuer les réactions endothermiques, permettant ainsi le stockage de l’énergie solaire intermittente en carburants sans émissions de CO2. Ce travail a pour objectif l’étude expérimentale de trois procédés solaires incluant la gazéification de biomasse, le reformage de méthane en boucle chimique, et la carboréduction de ZnO et MgO. La gazéification et le reformage permettent la valorisation de biomasse bois et de méthane en syngas, tandis que la carboréduction permet de produire Zn et Mg à partir de ZnO et MgO. Ces procédés ont été étudiés dans des réacteurs solaires de 1.5 kWth, en utilisant le rayonnement concentré fourni par des systèmes à concentration du laboratoire PROMES, Odeillo, France. L’impact des paramètres opératoires de chaque procédé sur les mécanismes réactionnels, conversion, rendement, et performances énergétiques a été évalué en détail. Ces procédés ont permis d’améliorer la conversion chimique, les rendements en syngas, les efficacités énergétiques tout en permettant un stockage de l’énergie solaire en combustibles transportables, avec des performances globales supérieures aux procédés conventionnels. De plus, leur faisabilité, fiabilité et robustesse pour la conversion de méthane et biomasse en syngas et la production de Mg et Zn en fonctionnement batch ou continu sous pression réduite ou atmosphérique en conditions solaires réelles ont été démontrés. / The investigated solar thermochemical processes consist of the thermochemical conversion of solid and gaseous carbonaceous feedstocks into syngas as well as metal oxides reduction into metal commodities utilizing concentrated solar energy to drive endothermic chemical reactions, thereby enabling intermittent solar energy storage into solar fuels and avoiding CO2 emissions. This work aims to experimentally investigate three key solar thermochemical conversion approaches regarding biomass gasification, chemical looping reforming of methane, and carbothermal reduction of ZnO and MgO. Solar gasification and solar chemical looping reforming allowed valorizing wood biomass and methane into syngas, while solar carbothermal reduction was applied to produce Zn and Mg from ZnO and MgO. Such solar thermochemical processes were performed in 1.5 kWth prototype solar chemical reactors, utilizing highly concentrated sunlight provided by a solar concentrator at PROMES laboratory, Odeillo, France. The impact of controlling parameters of each process on the reaction mechanism, conversion, yields, and process performance, during on-sun testing was investigated and evaluated thoroughly. Such processes were proved to significantly improve the chemical conversion, syngas yields, energy efficiency, with solar energy storage into transportable fuels, thereby outperforming the conventional processes. Moreover, their feasibility, reliability, and robustness in converting both methane and biomass feedstocks to syngas as well as producing Mg and Zn metals in batch and continuous operation under vacuum and atmospheric conditions during on-sun operation were successfully demonstrated.

Made available in DSpace on 2014-12-17T15:42:13Z (GMT). No. of bitstreams: 1 TiagoRC_DISSERT.pdf: 2194143 bytes, checksum: 2a20949c899c91ba3e574d7f71d319d4 (MD5) Previous issue date: 2012-04-11 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Oxygen carriers are metal oxides which have the ability to oxidize and reduce easily by various cycles. Due to this property these materials are widely usedin Chemical-Looping Reforming processes to produce H2 and syngas. In this work supports based on MCM-41 and La-SiO2 were synthesized by hydrothermal method. After the synthesis step they were calcined at 550?C for 2 hours and characterized by TG, XRD, surface area using the BET method and FTIR spectroscopy. The deposition of active phase, in this case Nickel, took place in the proportions of 5, 10 and 20% by weight of metallic nickel, for use as oxygen carriers.The XRD showed that increasing in the content of Ni supported on MCM-41 resulted in a decrease in spatial structure and lattice parameter of the material. The adsorption and desorption curves of the MCM-41 samples exhibited variations with the increase of Ni deposited. Surface area, average pore diameter and wall density of silica showed significant changes , due to the increase of the active phase on the mesoporous material. By other hand, in the samples with La-SiO2 composition was not observed peaks characteristic of hexagonal structure, in the XRD diffractogram. The adsorption/desorption isotherms of nitrogen observed are type IV, characteristic of mesoporous materials. The catalytic test indicates that the supports have no influence in the process, but the nickel concentration is very important, because the results for minor concentration of nickel are not good. The ratio H2/O2 was close to 2, for all 15 cycles involving the test storage capacity of O2, indicating that the materials are effective for oxygen transport / Transportadores de oxig?nio s?o ?xidos met?licos que possuem a capacidade de oxidar e reduzir facilmente por diversos ciclos. Devido a essa propriedade estes materiais s?o bastante utilizados nos processos de Chemical-Looping Reforming para a produ??o de H2 ou g?s de s?ntese (H2 mais CO). Neste trabalho foram sintetizados os suportes MCM-41 e La-SiO2 pelo o m?todo hidrot?rmico. Os materiais resultantes foram calcinados a 550 ?C por 2 horas e, posteriormente, caracterizados por TG, DRX, ?rea superficial pelo m?todo BET e FTIR. Ap?s a caracteriza??o dos suportes foi feita a deposi??o da fase ativa (Ni) com as propor??es de 5, 10 e 20% em massa de n?quel met?lico, para aplica??o como transportadores de oxig?nio. As an?lises de DRX mostraram que o aumento do teor de Ni suportado em MCM-41 deu origem a uma diminui??o no ordenamento estrutural e no par?metro de rede do material. As amostras MCM-41 apresentaram varia??es quanto ?s curvas de adsor??o/dessor??o de nitrog?nio, ?rea superficial, di?metro m?dio de poros e espessura da parede de s?lica, em fun??o do aumento da fase ativa no material mesoporoso. Enquanto que nas amostras com La-SiO2 n?o se observou picos caracter?sticos da estrutura hexagonal, nos difratogramas de DRX. Entretanto, as curvas de adsor??o/dessor??o de nitrog?nio observadas s?o do tipo IV, caracter?stico de materiais mesoporosos. Os resultados dos testes dos transportadores indicam que o suporte n?o influenciou no processo catal?tico. A raz?o H2/O2 foi pr?xima de 2, durante todos os 15 ciclos envolvendo o teste de capacidade de armazenamento de O2 , indicando que os materiais s?o eficientes para o transporte de oxig?nio estrutural e no par?metro de rede do material. As amostras MCM-41 apresentaram varia??es quanto ?s curvas de adsor??o/dessor??o de nitrog?nio, ?rea superficial, di?metro m?dio de poros e espessura da parede de s?lica, em fun??o do aumento da fase ativa no material mesoporoso. Enquanto que nas amostras com La-SiO2 n?o se observou picos caracter?sticos da estrutura hexagonal, nos difratogramas de DRX. Entretanto, as curvas de adsor??o/dessor??o de nitrog?nio observadas s?o do tipo IV, caracter?stico de materiais mesoporosos. Os resultados dos testes dos transportadores indicam que o suporte n?o influenciou no processo catal?tico. A raz?o H2/O2 foi pr?xima de 2, durante todos os 15 ciclos envolvendo o teste de capacidade de armazenamento de O2 , indicando que os materiais s?o eficientes para o transporte de oxig?nio