Limitations in the energy balance when VGO/aqueous bio-oil mixtures are co-processed in FCC units

The effect on the energy balance of a FCC unit after co-feeding the aqueous fraction of a bio-oil together with a vacuum gas oil (VGO) has been studied. The simulation program considers the interdependency relationship between the reaction and regeneration sections in the unit, where the heat of coke combustion has to sustain the energy requirements to preheat and vaporize the feedstock as well as the endothermic cracking reactions. The combustion of coke deposited on an equilibrium commercial FCC catalyst in cracking various bio-oil/VGO mixtures at 530 degrees C, with catalyst to oil relationships between 3 and 6 in a CREC Riser Simulator laboratory reactor, was investigated by means of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Results showed that the heat from coke combustion is not enough to provide the energy needed in the unit when the amount of bio-oil in the feedstock is larger than 5 wt%, mainly due to the high content of water in the aqueous fraction of the bio-oil and to the lower heat of combustion of the coke formed in co-processing, as compared to the VGO alone.This work has been carried out with the financial support of the Ministry of Science, Innovation and Universities (MICIU) of the Spanish Government (grant RTI2018-096981-B-I00) , the European Union's ERDF funds and Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie Actions (grant No 823745) and the Basque Government (grant IT1645-22) . The financial support of the Universidad Nacional del Litoral (UNL, Santa Fe, Argentina) , Proj. CAID 50420150100068LI, and Agencia Nacional de Promocion Cientifica y Tecnologica (ANPCyT) , PICT 1208/2016 is gratefully acknowledged

Yield of aromatics from naphthenics upon catalytic cracking

Cis- e trans decalina foram submetidas à reação com catalisadores de craqueamento, para estudar a formação de aromáticos numa fração particular de produtos líquidos do processo de craqueamento catalítico fluido (FCC). Um reator batelada em leito fluidizado, CREC, foi usado a 673 e 723 K com tempos de contato entre 3 e 15 s. Cis-decalina foi muito mais reativa. Apesar de diferenças induzidas e medidas na acessibilidade dos catalisadores, seus perfis de atividade foram similares, sugerindo que restrições difusionais não prevalecem. Os produtos foram hidrocarbonetos C1-C12, enquanto o coque foi muito baixo. Reações de isomerização, craqueamento, transferência de hidrogênio, abertura/contração de anel e alquilação ocorreram, e produtos das várias reações foram observados em tempos de reação muito baixos. Naftênicos bicíclicos C10 e aromáticos alquil-substituídos C7-C11 ou nafteno-aromáticos foram os produtos mais importantes. Um mecanismo de reação com três rotas iniciais (isomerização, abertura de anel e reações de transferência de hidrogênio) foi proposto. _________________________________________________________________________________________ ABSTRACT: Cis- and trans-decalin were reacted over cracking catalysts to study the formation of aromatics in a particular fraction of the liquid products obtained in the fluid catalytic cracking process (FCC). A batch, fluidized bed CREC riser simulator reactor was used at 673 and 723 K and contact times varied from 3 to 15 s. Cis-decalin was much more reactive. Despite differences induced and measured in their accessibility indices, the catalysts led to similar activity profiles, suggesting that diffusion restrictions do not prevail. Products were C1-C12 hydrocarbons while coke was very low. Isomerization, cracking, hydrogen transfer, ring opening, ring contraction and alkylation reactions occurred and products from the various reactions were observed at very short reaction times. Bicyclic C10 naphthenics and alkyl-substituted C7-C11 aromatics or naphtheno-aromatics were the most important products. A reaction mechanism with three initial routes (isomerization, ring opening and direct hydrogen transfer reactions) was proposed

Catalytic Cracking of Heavy Aromatics and Polycyclic Aromatic Hydrocarbons over Fluidized Catalytic Cracking Catalysts

The distribution of products in the range of gasoline and middle distillates cuts obtained in the catalytic cracking of heavy aromatics and polycyclic aromatic hydrocarbons over a FCC catalyst was studied. 1-Phenyloctane, biphenyl, fluorene, 9,10-dihydrophenanthrene, naphthalene, phenanthrene, pyrene and benz[a]anthracene were used as model compounds of alkylaromatic, naphthenic-aromatic and polyaromatic hydrocarbons which are present in VGO and residual feedstocks in the FCC process. The catalyst was used in its fresh and equilibrium forms at 450 ºC in a CREC Riser Simulator reactor with reaction times from 2 to 6 s. Thermal cracking reactions overwhelm the catalytic conversion of naphthenic-aromatic compounds such as fluorene and 9,10-dihydrophenanthrene. Under the same conditions, the fresh catalyst was more active than the equilibrium catalyst. The alkylaromatic, naphthenicaromatic and polyaromatic hydrocarbons, showed catalytic conversions which increased,were relatively stable and decreased, respectively, as a function of reaction time. The distribution of products suggested that most important reactions were thermal dehydrogenation, hydrogen transfer, ring opening, cracking and condensation. It was shown that all the model compounds are cracked, yielding particularly benzene in the gasoline range and coke.Fil: Pujro Tarquino, Richard Alfonzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Falco, Marisa Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Production of aromatic compounds in the heavy naphtha and light LCO ranges: Catalytic cracking of C10 naphthenic-aromatics and aromatics

BACKGROUND: The conversions of bicyclic compounds, both a naphthenic-aromatic compound (tetralin) and an aromatic compound (naphthalene), as model reactants representative of the heavy gasoline and light cycle oil (LCO) cuts in fluid catalytic cracking (FCC), were studied to understand the formation of C10–C20 aromatic compounds in gasoline and middle distillates cuts, in view of their impact on the properties of the cuts. A commercial FCC catalyst was used in its fresh, hydrothermally de-aluminated and equilibrium forms, at 450 °C in a fluidized bed CREC Riser Simulator reactor in the 2–8 s reaction time range. RESULTS: Products were C1–C14 hydrocarbons and coke. Based on the product distributions, reaction networks were proposed for both reactants. The reactions considered in the networks were hydrogen transfer, cracking, ring opening and contraction, alkylation and disproportionation. CONCLUSION: The load of zeolite in the catalysts and their acidities have the strongest influences on reaction selectivities. In the case of tetralin, the prevalent reaction is hydrogen transfer, which becomes more important as the catalysts are less active, the hydrocarbons with highest yields being C10 aromatics. Cracking reactions predominate in naphthalene conversion over all the catalysts, a fact which favors mono-aromatic C9− hydrocarbons. These results can help in the design of new FCC catalysts with better selectivity control.Fil: Pujro Tarquino, Richard Alfonzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Falco, Marisa Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Formation of aromatics in heavy gasoline and light LCO ends in FCC

Decalin, a naphthenic bicyclic compound, was reacted over a commercial FCC catalyst in its fresh, equilibrium and three dealuminated forms in order to analyze the formation of aromatic hydrocarbons in the gasoline and LCO cuts, heavy and light ends, respectively. A batch, fluidized bed CREC Riser simulator laboratory reactor was used at 450 ºC with short contact times from 1 to 8 s. The dealuminated catalysts showed an activity intermediate between those of the fresh and equilibrium catalysts, which can be correlated to zeolite content and acidity. Also those properties, at least in the range of values observed in this work, seem to be the most important characteristic in controlling the selectivity of the set of reactions. A reaction network was described, where hydrogen transfer reactions are considered to be the most important to form aromatics, a fact which is essentially unavoidable when a bicyclic naphthenic is converted on these catalysts. Aromatic belonged mainly to the gasoline boiling point range and, to a lower extent, to LCO.Fil: Pujro Tarquino, Richard Alfonzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Falco, Marisa Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Reactivity of the saturated, aromatic, and resin fractions of ATR resids under FCC conditions

SARA (saturate, aromatic, resin and asphaltene) fractions composing an atmospheric tower resid from a naphthenic crude were separated using the ASTM 2007 method. Two commercial equilibrium catalysts, of the conventional and resid types, were used to convert the aromatic, resin and saturate fractions under conditions of the FCC process. The reaction experiments were performed in a CREC Riser Simulator reactor. Reaction temperature was 550 °C, reaction times were from 5 to 20 s, the catalyst mass was 0.8 g and the catalyst to oil relationship was 5.0. The various fractions were used dissolved in toluene at 20 wt.%. The hydrocarbon reaction products were grouped into dry gas, LPG, compounds in the gasoline and LCO boiling ranges and coke. All the fractions converted almost completely, but differences in the yields of the main hydrocarbon groups were observed which revealed the fractions’ nature.Fil: Pujro Tarquino, Richard Alfonzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Falco, Marisa Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Devard, Alejandra Veronica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Hydrogen Transfer between Hydrocarbons and Oxygenated Compounds in Coprocessing Bio-Oils in Fluid Catalytic Cracking

Oxygenated model compounds representing typical components of bio-oils and a hydrocarbon hydrogen donor agent were used to study hydrogen transfer reactions between hydrocarbons and oxygenated compounds when coprocessed over acidic commercial fluid catalytic cracking (FCC) catalysts. Phenol, syringol, and trimethoxybenzene were each mixed withtetralin at 5 wt % individually in benzene as an inert solvent. The mixtures were reacted in a fluidized bed, batch CREC Riser Simulator laboratory reactor during 10 s contact time with a catalyst to oil relationship of 3 at 500 °C over a commercial equilibrium FCC catalyst, conditions being selected in order to simulate FCC bio-oil−vacuum gas oil coprocessing. Tetralin was also reacted alone at 5 wt % in benzene to gather background information. When tetralin was the only reactant, its conversion was 87%, the most important reactions being hydrogen transfer, as shown by the yield of naphthalene, and cracking. Alkylation and disproportionation were also observed to a lower extent. In the experiments with the mixtures, the oxygenated compounds converted completely and tetralin converted to less than half the conversion when pure. In these experiments, as compared to pure tetralin, the yield of gases and C11+ hydrocarbons increased and the yield of coke decreased, showing the interaction between the hydrocarbon and the model oxygenated compound reactants. The index SHT, which shows the selectivity to hydrogen transfer reactions from tetralin, increased significantly, to about 2 times, in the experiments with the mixtures. Moreover, coke from pure tetralin was shown to be qualitatively different from that in the experiments with the mixtures, where it was more condensed, thus confirming that the reaction pathways are dissimilar.Fil: Pujro Tarquino, Richard Alfonzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Panero, Melisa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Bertero, Melisa Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Falco, Marisa Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Review on Reaction Pathways in the Catalytic Upgrading of Biomass Pyrolysis Liquids

Bio-oils are the liquid products from the pyrolysis of biomass, which captured pronounced attention and showed relevance as an alternative source of fuels and chemicals. Bio-oils are complex mixtures of a large number of components, mostly oxygenated compounds, including many different chemical functionalities, which require upgrading (removal of oxygen) to be useful as fuels. As acid or bifunctional metal/acid catalysts are used in upgrading, the components in the mixture will be subjected to many different chemical reactions, including, among others, decarboxylation, decarbonylation, dehydration, demethoxylation, hydrogenation, dehydrogenation, cracking, isomerization, and hydrogen transfer. Purely thermal reactions are also to be produced in upgrading processes. Thus, the set of chemical reactions is exceptionally intricate. This review provides broad information about the mechanisms of numerous reactions which can take place, based on a transversal view, that is, the emphasis is posed on the reactions and the corresponding descriptions embrace the different chemical groups.Fil: Pujro Tarquino, Richard Alfonzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: García, Juan Rafael. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Bertero, Melisa Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Falco, Marisa Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Hydrocarbon Yield Structure in the Conversion of Heavy Model Molecules (Quinolin-65) on Fluidized Catalytic Cracking Catalyst

The reactivity of a heavy model molecule (quinolin-65, named Q65, a 2,3,7,8-dibenzopyrene derivative) over two different equilibrium fluidized catalytic cracking catalysts of the conventional and resid types was studied at 550 °C and with reaction times that varied from 5 to 20 s, in a batch fluidized-bed laboratory reactor. Two types of experiments were performed to determine the hydrocarbon products resulting from the conversion of Q65. This compound is solid at room temperature, and a solution of Q65 at 4.6 wt % in toluene and pure toluene were used. Conversions and yields were assessed by means of careful mass balances. The product distributions showed that Q65 produced a wide range of hydrocarbons from C1 to C20. These distributions were different according to the formulations of the catalysts. Olefins were predominant among gases and, neatly, aromatics among liquids. Coke yields were high, exceeding 12 wt %. The characteristics of the catalysts were also revealed through the higher activity and hydrogen-transfer ability of the conventional catalyst and the better coke selectivity of the resid catalyst. It was shown that both the linear alkyl chain and the multi-ring core react.Fil: Devard, Alejandra Veronica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Pujro Tarquino, Richard Alfonzo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: de la Puente, Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Microwave-assisted production of biochar from oil palm mesocarp fiber and its dye removal properties

Malaysia is one of the largest producers of palm oil in the world, which inevitably would also result in huge production of oil palm biomass. Without proper management, this biomass could pose serious environmental problems. Oil palm mesocarp fiber (OPMF) is one type of oil palm biomass which can be processed further for useful application such as dye removal from water. In the present study, OPMF was thermally treated using microwave-assisted pyrolysis. The sample was characterized (proximate, ultimate, lignin content, BET, FTIR, and SEM) and investigated using thermogravimetric analyzer. The activation energy and pre-exponential factor achieved from the Kissinger, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW) methods were 159.74, 161.90, 163.29 kJ mol−1, and 1.02 × 10−10, 1.90 × 10−13, 3.79 × 10−17 min−1, respectively. The dye removal performance was evaluated using methylene blue (MB) with parameters of initial concentration of MB, contact time, biochar dosage, temperature and pH. The kinetics of MB removal by OPMF was best described using the pseudo-second order kinetic model, followed by Elovich, pseudo-first order and Weber-Morris. As a conclusion, OPMF generated from oil palm processing has the potential to be used as alternative raw materials to produce biochar for dye removal application