FCC testing at bench scale: New units, new processes, new feeds

As the FCC process has evolved over decades, several laboratory scale equipment have appeared to maintain a proper assessment of catalysts activity. Several laboratory equipments are available for simulating the FCC process, from the well known fixed bed, MicroActivity Test to newer, fluid bed or transported bed units. As well, a number of units have been created to simulate other parts of the process such as regenerator or stripper, The increased pressure for treating non-conventional feeds, from reprocessing gasoline to extra-heavy feeds or oils produced from biomass containing large amounts of heteroatoms, increase the needs to have a laboratory test which is as close as possible to the process so that data extraction from the laboratory test are simplified, thus less prone to errors or misunderstanding.Financial support by MICINN (Consolider-Ingenio 2010 MULTICAT) and MINECO (Project MAT2011-29020-0O2-02 and Subprogram for excellence Severo Ochoa, SEV 2012 0267) is gratefully acknowledged.Corma Canós, A.; Sauvanaud, LL. (2013). FCC testing at bench scale: New units, new processes, new feeds. Catalysis Today. 218-219:107-114. doi:10.1016/j.cattod.2013.03.038S107114218-21

Synthesis of hybrid gasoline by FCC co-processing of crude oil distillates and bio-oils obtained from bio-mass fast pyrolysis

La pyrolyse de la biomasse ligno-cellulosique permet la production de bio-huiles dans la perspective à court terme de carburants hybrides contenant une fraction de bio-carbone dans un carburant conventionnel d'origine fossile (essence ou diesel). Cependant, la forte concentration en oxygène dans ces huiles, leur instabilité et faible densité énergétique (comparée aux carburants fossiles) imposent des pré-traitements permettant cette co-synthèse de carburants hybrides. Ainsi, après hydrotraitement ou ajout d’un catalyseur durant la pyrolyse, ces bio-huiles peuvent être mélangées à un distillat du pétrole en vue de développer des carburants hybrides conformes aux normes européennes. Les travaux de cette thèse sont centrés sur la production d'essences hybrides par craquage catalytique. L'objectif principal est d'évaluer l'impact de la qualité des bio-huiles (nature de la pyrolyse, niveau d'hydrotraitement, ajout de catalyseurs) sur la qualité des essences produites (rendements, aromaticité, présence de résidus oxygénés etc) en présence d'une charge pétrolière de type distillat sous vide. Un réacteur en lit fixe, de type MAT, simule les conditions de fonctionnement d’une unité FCC de craquage catalytique à 500°C. Les principaux résultats sont les suivants:Une approche mécanistique indique que la conversion désoxygénante des molécules oxygénées de la bio-huile induit une surconsommation de l’hydrogène extrait des hydrocarbures lors du craquage, aboutissant à une forte concentration d’aromatiques et d'insaturés ainsi qu'à une formation excédentaire de coke. Les réactions de craquage des fragments ligno-cellulosiques des bio-huiles concernent essentiellement les sites acides extérieurs au réseau zéolithique, ce dernier permettant les transferts d'hydrogène à partir de l'intérieur du réseau où s'opère le craquage des hydrocarbures. L'incapacité à craquer certains dérivés légers de type phénoliques explique les traces de ces composés dans les essences hybrides produites. L’utilité d’un hydrotraitement couteux des huiles de pyrolyse thermique est discutée en regard d'une pyrolyse catalytique, moins onéreuse, qui produit autant de bio-huile et conduit à une production d’essence hybride équivalente, quoique que plus riche en dérivés phénoliquesBio-oils can be produced by pyrolysis of ligno-cellulosic biomass. These bio-oils open the possibility for hybrid fuels, regular fossil fuels containing a fraction of biocarbon. The high concentration of oxygen in these bio-oils, their instability and low energy density (compared to liquid fossil fuels) require a pre-processing step before the conversion to hybrid fuels. After a hydrodeoxygenation (HDO) step or by catalytic upgrading during pyrolysis, these bio-oils can be blended with petroleum fractions to convert them into hybrid fuels in line with European regulations. The study presented in this thesis is focused on the production of hybrid gasoline by catalytic cracking. The aim is to evaluate the impact of the bio-oil nature, up-grading and content (type of pyrolysis, level of de-oxygenation, catalysts types) on the quality of the gasoline (yields, aromatic nature, presence of oxygenated molecules) by catalytic cracking of these bio-oils with vacuum gasoil (VGO). A MAT type fixed bed reactor is used to mimic the conditions of an industrial FCC (Fluid catalytic cracking) unit. The main results are: 1) A mechanistic approach shows that the conversion of oxygenated molecules from the bio-oil lead to an extra consumption of hydrogen extracted from the hydrocarbons during cracking, resulting in a high concentration of aromatics and unsaturated hydrocarbons and in the formation of large amounts of coke. 2) Cracking of lignin fragments takes place mainly on the acid sites located at zeolites surface. This involves a hydrogen transfer from hydrocarbon reactions inside the zeolites. Small phenolic molecules do not crack under these conditions and are found in the gasoline fraction. 3) Co-processing of bio-oils produced by catalytic upgrading during pyrolysis lead to similar gasoline yields and quality besides a slightly higher fraction of phenolics. This route seems to constitute an alternative to the costly HDO step for the thermally produced bio-oil

Synthesis of hybrid transportation fuel: mechanism and fuel quality

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Hybrid transportation fuel from hydrodeoxygenated or catalytic pyrolysis oil co-processing: mechanism and fuel quality

International @ INGENIERIE+GFO:YSC:CMIInternational audienceNon

The fate of bio-carbon in FCC co-processing products

INGENIERIE+GFO:NTE:YSC:CMIA promising alternative to the first generation of bio-fuels is to produce mixed bio- and fossil fuels by co-processing mixtures of biomass pyrolysis oil with crude oil fractions obtained from distillation in a conventional oil refinery. This was demonstrated to be technically feasible for fluid catalytic cracking (FCC), which is the main refinery process for producing gasoline. However, co-processing leads to more coke formation and to a more aromatic gasoline fraction. A detailed understanding is necessary on how the oxygenated moieties effect the reaction mechanism to further improve the process/catalysts. Moreover, for technical and marketing reasons, it is absolutely required to accurately determine the proportion of renewable molecules in the commercialized products. The carbon-14 method (also called radiocarbon or C-14) has been used as the most accurate and powerful method to discriminate fossil carbon from bio-carbon, since fossil fuel is virtually C-14-free, while biofuel contains the present-day "natural" amount of C-14. This technique has shown that not all FCC products share bio-carbon statistically. The coke formed during a FCC cycle and to a lesser extent the gases are found richer in C-14 than gasoline. This result gives valuable information on the co-processing mechanism, supporting that the bio-oil oxygenated molecules are processed more easily at the expenses of the crude oil hydrocarbons, favouring the bio-coke and the bio-light gases production

Tomorrow's biofuels: hybrid bio-gasoline production in FCC units

INGENIERIE+YSC:CMINon

The fate of bio-carbon in FCC co-processing products

International @ INGENIERIE+YSC:CMIInternational audienceNon

Tomorrow's biofuels: hybrid bio-gasoline production in FCC units

INGENIERIE+YSC:CMINon

The fate of bio-carbon in FCC co-processing products

International @ INGENIERIE+YSC:CMIInternational audienceNon

Analytical techniques tailored for biomass transformation to biofuels

RAFFINAGE:INGENIERIE+GFO:CLO:GTU:NTE:YSC:CMIAn analytical platform was developed for the detection of biomass oxygenates and biocarbon in biogasoline produced by coprocessing of hydrodeoxygenated pyrolysis oils (HDO-oil) and vacuum gas oil. A combination of different analytical techniques is necessary for analyzing such complex mixtures. The presence of various oxygenated compounds such as alcohols, acids, and phenols was quantified using phosphorus nuclear magnetic resonance spectroscopy. Different alkylphenols were identified using two-dimensional gas chromatography-mass spectrometry. The transformations of lignin oligomers present in HDO-oil were determined with size-exclusion chromatography carried out for the products. Accelerator mass spectrometry was used to make the distinction between carbonaceous material of biological origin and that of fossil origin. This type of analytical platform, which is tailored for bio-oil identification and quantification, appears to be required for exploratory catalyst research and kinetic studies in this rapidly expanding domain. (c) 2011 American Institute of Chemical Engineers Environ Prog, 32: 377-383, 201