Conversion of waste plastics into fuels: Recycling polyethylene in FCC

Low density polyethylene was dissolved into toluene and converted at 500 °C over three different commercial FCC catalysts in a laboratory Riser Simulator reactor. Short reaction-times up to 12 s were used. All the catalysts had qualitatively similar behaviors. The specific contribution of the polymer to the product slate of FCC was centered in hydrocarbons in the range of gasoline, with high aromatic content and highly olefinic C3–C4 gases. Saturated C4–C5 products were mainly isoparaffins. The additional coke formed by the polymer would make coke yields to increase moderately in relation to the standard operation. These facts confirmed that this recycling option, which is based on a proven technology, represents an interesting alternative to solve a major environmental problem.Fil: 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: Klocker, C.. 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

FCC Matrix Components and Their Combination with Y Zeolite to Enhance the Deoxygenation of Bio-oils

The immediate catalytic conversions of pyrolytic bio-oils from pine sawdust and soybean shell over mesoporous catalysts (silica, alumina, and silica-alumina) and their combinations with Y zeolite, were studied. The effect of mesoporosity and acidity on the bio-oil deoxygenation and conversion into hydrocarbons was investigated. Pyrolysis and immediate catalytic conversion of bio-oil were performed in an integrated pyrolysis–upgrading reactor, for 7 min under a 30-ml/min flow of nitrogen at 550 °C. Important differences were observed in the conversion of the bio-oils, according to the composition of the raw biomasses. Pine sawdust bio-oil produced more coke and less hydrocarbons in the range of gasoline than soybean shell bio-oil over all the catalysts. Mesoporous catalysts showed conversion and deoxygenation between 14 and 29 percentage points higher with the more acidic solid (SiO2-Al2O3) in the case of pine sawdust bio-oil and between 2 and 10 percentage points higher with the solid having the highest specific surface area (SiO2) in the case of soybean shell bio-oil. Among the compound catalysts, the best performance for the case of pine sawdust corresponded to the catalyst with the highest mesoporosity (Y/SiO2), while for soybean shell corresponded to the most acidic catalysts (Y/Al2O3 and Y/SiO2-Al2O3). Soybean shell bio-oil showed more low molecular weight compounds (less than 130 g mol−1), which diffuse more easily in the zeolite channels, thus favoring conversion and deoxygenation mechanisms. On the contrary, for pine sawdust bio-oil, the surface area contributed by the mesopores in the matrix played a key role in pre-cracking bulky molecules.Fil: 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: 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: 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

Performance of Equilibrium FCC Catalysts in the Conversion of the SARA Fractions in VGO

Two equilibrium FCC catalysts of the octane-barrel (ECAT-D) and resid (ECAT-R) types were used in the cracking of a typical vacuum gasoil (VGO) and its saturated (SF), aromatic (AF), and resin (RF) fractions. The experiments were carried out in a batch, fluidized bed laboratory CREC Riser Simulator reactor. The reaction temperature was 500 °C, the catalyst-to-oil relationship was 1, with 0.2 g of the catalyst being used in each experiment, and the reaction times were 0.7, 1.5, and 3 s. The ranking of the reactivities of the different feedstocks was SF > VGO > AF > RF over both catalysts. While the AF and RF fractions yielded more gasoline than the SF fraction, the latter showed the highest yields of LPG. The coke forming trend followed the order SF < VGO < AF < RF. Even though catalyst ECAT-D, with a higher and stronger acidity, was more active than catalyst ECAT-R, which has less acidity and better textural properties (higher mesoporosity and pore diameter), the latter was less affected by coke deposition, considering the changes in the specific surface area and acidic properties after use. Coke impacted more severely on Bronsted acid sites than on Lewis sites, particularly when the AF and RF fractions were used. The stronger acid sites were more severely affected by coke, particularly in catalyst ECAT-D. The negative effect on strong acidic sites was consistent with the increasing basic character of the feedstocks, following the order SF < VGO < AF < RF.Fil: Fals Guerra, Jayson. 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: 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

The influence on selectivity of the aluminum content in the matrix of FCC catalysts

The influence that both the type of matrix and the interaction between zeolite and matrix have on the selectivity of FCC catalysts was studied by means of the conversion of cyclohexene at 300 ◦C on a large number of samples in which the matrix was changed. Silica/alumina matrices had 0, 12 and 25% of alumina, and catalysts were subjected to steaming of varying severity followed by acid extraction in some samples to remove extraframework aluminum species (EFAl). Resulting  catalysts were characterized by various techniques. It was confirmed that hydrogen transfer does not depend directly on the type of coordination of the aluminum atoms in the sample, but rather on the density of paired sites in the zeolite component. It was possible to define the selectivity of reaction pathways (SRP) as an index to describe the relative importance of the processes ofdesorption via hydride transfer to yield cyclohexane against retention of the cation cyclohexil via isomerization and further reaction. A high value of SRP would mean that a given catalyst has a lower ability to retain adsorbed species that can be subjected to additional reactions like, in this particular reaction, isomerization and further proton transfer to the catalyst surface, or cracking. The index was shown to increase whereas the relative amount of octahedral aluminum atoms decreased, a fact that can be associated to the formation of a new silica/alumina phase. Such phase would be formed by means of the reaction of aluminum extracted from the zeolite upon steaming and silica present in the matrix.Fil: 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: Falabella Sousa Aguiar, Eduardo. Centro de Pesquisas-Petrobras; BrasilFil: Figueiredo Costa, Alexandre. Centro de Pesquisas-Petrobras; BrasilFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; Argentin

Bio-composite Films Based on Alginate and Rice Husk Tar Microparticles Loaded with Eugenol for Active Packaging

This work focused on the valorization of tar derived from rice husk pyrolysis as a precursor of matrices for the encapsulation of active principles. In this regard, the development of novel films based on alginate and eugenol-loaded tar microparticles with suitable mechanical properties and antibacterial activity was studied. Tar microparticles loaded with eugenol were incorporated into sodium alginate films and the effect on the mechanical, thermal and humidity resistance properties were determined, as well as the antimicrobial activity. Films with different crosslinking degrees were also prepared using CaCl2, and the eugenol controlled release profiles were evaluated. Crosslinked films exhibited improved mechanical and humidity resistance properties, as well as a lower release rate of eugenol in water. The antimicrobial studies showed that eugenol-loaded films present a higher antimicrobial activity against Staphylococcus aureus. Alginate/eugenol-loaded tar microparticles composites showed an enhancement of antibacterial properties and suitable physical characteristics to be used in active packaging applications.Fil: Taverna, María Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina. Universidad Tecnológica Nacional. Facultad Reg.san Francisco. Departamento de Ingeniería Química; ArgentinaFil: Busatto, Carlos Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Saires, Paula Judith. 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: Estenoz, Diana Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentin

Operation of FCC with mixtures of regenerated and deactivated catalyst

The operation of FCC with mixtures of coked and regenerated catalyst was studied with a riser simulator reactor on two equilibrium catalysts at 550◦C. The coked catalysts maintain an activity level that enables them to be used in the mixtures. The catalytic performances of the regenerated catalysts were used as references against which the behaviors of 25:75 and 50:50 (coked:regenerated) mixtures were compared. It was observed that overall catoil has to be increased to maintain conversion. While the yields of gases, gasoline and LCO showed to be independent of the operative mode, changes were observed in the selectivity to light olefinsC4?C6that are mainly due to changes in the yields of the isoparaffins in the groups. In turn, these changes could be the consequence of the resulting density of paired acid sites in the zeolite components on hydrogen transfer reactions, due to the contributions by the coked and regenerated portions of catalysts. Coke yields in mixtures of coked and regenerated catalysts are not higher, which would allow increasing catalyst circulation without impacting on heat balance. The  particularities of this new operation of FCC are very dependent on catalyst properties.Fil: Spretz, R.. 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

Conversion of pine sawdust bio-oil (raw and thermally processed) over equilibrium FCC catalysts

A raw bio-oil from pine sawdust, the liquid product from its thermal conditioning and a synthetic bio-oil composed by eight model compounds representing the main chemical groups in bio-oils, were converted thermally and over a commercial equilibrium FCC catalyst. The experiments were performed in a fixed bed reactor at 500 C. The highest hydrocarbon yield (53.5 wt.%) was obtained with the conditioned liquid. The coke yields were significant in all the cases, from 9 to 14 wt.%. The synthetic bio-oil produced lesser hydrocarbons and more oxygenated compounds and coke than the authentic feedstocks from biomass. The previous thermal treatment of the raw bio-oil had the positive effects of increasing 25% the yield of hydrocarbons, decreasing 55% the yield of oxygenated compounds and decreasing 20% the yield of coke, particularly the more condensed coke.Fil: Bertero, Melisa Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera"; ArgentinaFil: Sedran, Ulises Anselmo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones En Catalisis y Petroquímica "ing. Jose Miguel Parera"; Argentin

Use of stirred batch reactors for the assessment of adsorption constants in porous solid catalysts with simultaneous diffusion and reaction. Theoretical analysis

A simple, pseudo-equilibrium model was derived for a catalytic system with a first order chemical reaction and simultaneous diffusive and adsorptive processes, in order to assess the corresponding kinetics and Henry law's-type adsorption parameters. Solutions from this model were compared to exact solutions from a more detailed, general model. It was shown that under most of the experimental conditions used in stirred batch reactors and the usual model considerations, it is only possible to assess apparent adsorption parameters. Also, we observed that a stable relationship between the concentrations in the gas and solid phases is reached. The error produced in assuming that the apparent adsorption constant is the real one was calculated to be very important. The value of the apparent adsorption constant depends on various system properties and experimental conditions, such as the Thiele modulus, the amount of catalyst and the contact time. The ratio between the apparent and real adsorption constants was shown to be the transient effectiveness factor at any moment. This ratio reaches a maximum value for the pseudo-equilibrium state, that is always larger than the steady-state effectiveness factor, becoming closer as long as the system's adsorption capacity decreases. The analysis determines the operative conditions to reduce the parametric correlation. Also a criterion for the applicability of usual approximations in the assessment of kinetics and equilibrium adsorption parameters in porous solid catalysts by means of pulse injection methods is established.Fil: Bidabehere, Claudia María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; 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

Simultaneous diffusion, adsorption, and reaction in fluid catalytic cracking catalysts

Simultaneous diffusion, adsorption, and reaction that take place inside the zeolitic component of equilibrium commercial fluid catalytic cracking (FCC) catalysts were described by means of heterogeneous models. n-Hexadecane was used as a test reactant at high temperatures (440-550°C) over two different equilibrium catalysts under very short contact times up to 10 s in a Riser Simulator reactor. The system's parameters were obtained by fitting the model to the reactant's gas-phase concentration versus reaction time data. When zeolite intracrystalline diffusion was first assumed as the controlling mechanism for mass transfer, its energy of activation resulted close to the heat of adsorption, suggesting that diffusion in the zeolite micropores could be indeed controlling. The solution under this new approach led to the obtention of parameters that were consistent with the existence of strong diffusion limitations for the reaction and with lower activity in the low unit cell size catalyst. Diffusion, which would be a nonactivated process, had coefficients that were essentially the same in both catalysts, while the energies of activation of the reaction were different and reflected the higher relative importance of the mechanism of monomolecular cracking in the more dealuminated catalyst. The need for a careful assessment of adsorption parameters in FCC catalysts was confirmed by the fact that their magnitudes change significantly as a function of temperature, with adsorption being somewhat stronger on the higher unit cell size catalyst in the temperature range of interest for FCC. The method employed proved to be adequate and sensitive for the quantification of these issues, which are important in reactor design and simulation and catalyst evaluation procedures.Fil: Bidabehere, Claudia María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; 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

Recycling of waste plastics into fuels. LDPE conversion in FCC

In order to study the tertiary recycling of waste polymers in standard FCC units low density polyethylene (LDPE) was dissolved into a commercial vacuum gas oil at 2 and 6 wt.% and converted over two equilibrium FCC catalysts of the octane-barrel and resid types in a CREC Riser Simulator laboratory reactor. The reaction temperatures were 500, 525 and 550 ◦C, the mass catalyst to oil relationship was 6.35 and the contact times were from 3 to 30 s. The study included the effect of the concentration of LDPE over conversion, the various product (dry gas, LPG, gasoline, LCO and coke) yields and selectivities. Results were very similar for the two concentrations. At typical conversions of 70 wt.%, dry gas and gasoline yields increased about 10 wt.%, LPG yields between 9 and 13 wt.%, LCO yields decreased more than 15 wt.% andcoke yields were lower than 7.7 wt.% The RON index of gasoline was improved slightly (up to one point), mainly due to significant increases in olefin concentrations, while the fuel quality of the LCO cut was not affected. LDPE is easily converted and seems to be subjected to primary reactions of catalytic cracking, thus increasing the yields of olefins in the LPG and gasoline boiling ranges. It was concluded that recycling waste LDPE by co-processing it as part of conventional feeds to the FCC would not interfere with the standard operation.Fil: Passamonti, Francisco Javier. 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