Estudio de la actividad del catalizador circulante en la unidad de craqueo catalítico fluidizado (FCC) de la Refinería Estatal Esmeraldas (REE)

In the oil industry the fluidized catalytic cracking unit (FCCU) aims to increase the yield of gasoline production and improve efficiency in the processing of crude oil. The determination of the circulating catalyst activity is a very important parameter, which evaluates the performance of the catalyst. It is also helpful to quantify the amount of fresh catalyst that must be added in the process in order to maintain the activity constant (equilibrium). The Esmeraldas State Refinery (REE) does not have the necessary infrastructure for the reliably selection and characterization of catalytic behavior. Therefore, this thesis proposes the design and construction of a Test Catalyst Equipment (TCE) for fluidized bed reactions. The work consists of the theoretical design considerations for the manufacture of a laboratory reactor. Subsequently, the real size of reactor is calculated based on the fluidization experiments by ejection. Additionally, in order to find a potential catalyst for large molecules a meso-porous solid (MMP) is synthesized. Such material is made from of amorphous alumino-silicate, which is subjected to a partial crystallization process of zeolite ZSM-5 in order to increase their activity. The used method is hydrothermal synthesis, i.e. self-generated pressure from water in a closed reactor. The catalyst equilibrium activity of the three samples taken from FCC Unit of Esmeraldas Refinery evaluated in the TCE indicated an activity of 81%, 79% and 78%. Meanwhile, MMP synthesized catalyst material has an activity of 64%, with a comparable composition gaseous of the product to the commercial catalyst used at the refinery, supplied by Grace Davison Company.En la industria del petróleo la unidad de craqueo catalítico fluidizado (FCCU) tiene como propósito incrementar el rendimiento en la producción de gasolinas así como mejorar la eficiencia en la transformación del crudo. La determinación de la actividad del catalizador que circula en una unidad de craqueo catalítico fluidizado es un parámetro de gran importancia, que permite evaluar el comportamiento del catalizador. Además es de ayuda para cuantificar la cantidad de catalizador fresco que se debe adicionar en el proceso con el objeto de mantener la actividad en equilibrio. Siendo que la Refinería Estatal de Esmeraldas (REE) no dispone de la infraestructura necesaria para el proceso de selección y caracterización del comportamiento catalítico de manera confiable, la presente tesis propone el diseño y construcción de un equipo para prueba de catalizadores en lecho fluidizado (Testing Catalyst Equipment, TCE). El trabajo consiste en realizar las consideraciones teóricas de diseño para la fabricación de un reactor a nivel de laboratorio. Posteriormente, y tomando como base la experimentación de fluidización por eyección; se obtienen datos que permiten calcular las dimensiones reales del reactor. Adicionalmente, con el fin de encontrar un potencial catalizador para moléculas grandes, se sintetiza un sólido meso-poroso (MMP). Dicho material está formado a partir de una base de alumino-silicato amorfo, el cual se somete a un proceso de cristalización parcial de zeolita ZSM-5 con el objeto de aumentar su actividad. El método de síntesis utilizado es el hidrotermal, es decir, bajo presión autogenerada a partir de agua en un reactor cerrado. La actividad del catalizador de equilibrio de las tres muestras tomadas de la unidad FCC en la Refinería Estatal Esmeraldas evaluadas en el TCE indica una actividad de 81%, 79% y 78%. Entre tanto, el material MMP sintetizado como catalizador presenta una actividad del 64 %, con una composición gaseosa comparable a la obtenida con el catalizador comercial, suministrado por la Grace Davison Company, utilizado en refinería

Characterization of liquid fraction obtained from pyrolysis of post- consumer mixed plastic waste: A comparing between measured and calculated parameters

This work has received funds from the Universidad de Granada/CBUA project PID2019-108826RB-I00/SRA (State Research Agency) /10.13039/501100011033.In this study, thermal pyrolysis of a real mixture of plastic wastes collected from municipal solid waste of Granada (Spain) was performed to obtain a liquid oil. The goals of the present study were: 1) identify the optimal conditions to obtain maximum yields of the liquid fraction, 2) experimentally measure basic characteristic parameters of pyrolytic oils, 3) use correlations or equations used in the hydrocarbon industry to estimate the measured properties, 4) make a comparison between the measured and calculated properties by predictive mathematical expressions, 5) develop new correlations for estimating pyrolytic oil properties. As main results, the optimal temperature to obtain maximum yield of liquid fraction was 500 °C. The physical and chemical properties of pyrolytic oils changed as temperature increased due to the presence of hydrogenation and dehydrogenation reactions. Also, the approximation of the chromatography data allowed to determine, by simulated distillation, the potential fuel yields that will be obtained if processed as synthetic crude in an atmospheric tower and a vacuum tower. Finally, two novel modified equations were proposed to estimate the specific gravity and refractive index parameter for pyrolytic oils.Universidad de Granada/CBUA project (State Research Agency) PID2019-108826RB-I00/SR

Characterization of the Different Oils Obtained through the Catalytic In Situ Pyrolysis of Polyethylene Film from Municipal Solid Waste

This work is part of the project PID2019-108826RB-I00 funded by MCIN/AEI/10.13039/501100011033.Nowadays, the thermal and catalytic decomposition of plastic wastes by pyrolysis is one of the best alternatives to convert these wastes into quality fuel oils, thus replenishing some petroleum resources. This work studied the catalytic pyrolysis of polyethylene film waste from the remaining organic fraction on different catalysts under dynamic operating conditions in a batch reactor. These catalysts have been characterized through isotherms of adsorption-desorption with N2 and X-ray powder diffraction for structural characterization to see the differences in their use. The results obtained have been compared with the pyrolysis of the same material without a catalyst. Special attention has been paid to the similarities and differences with thermal pyrolysis. The characterization of the liquid fraction, including physical and chemical properties, has been carried out. The liquid yield varies from 37 to 43%; it has good calorific values of 46–48 MJ/kg, an average density of 0.82 g/cm3, and a fairly low viscosity compared to the product without the catalyst. Other properties like the American Petroleum Institute (API) gravity or pH were also determined and found to be similar to conventional fuels. Oils are mainly composed of paraffins, naphthenes, and aromatic hydrocarbons. The general distribution of carbons is C7 to C31. Finally, a detailed analysis of the composition of liquid products shows they present heavy naphtha, kerosene, and diesel fractions in different proportions in the function of the catalyst used.PID2019-108826RB-I00MCIN/AEI/10.13039/50110001103

Towards fuels production by a catalytic pyrolysis of a real mixture of post-consumer plastic waste

The contribution provides a valorization alternative for rejected plastic wastes from mechanical-biological treatment (non-recyclable material) via an in-situ catalytic pyrolysis process focused on the production of a liquid fraction with similar properties to traditional fuels (i.e., gasoline, kerosine, and diesel). According to the ASTM recommendations, on small samples without prior physical separation, fuel fraction identification was carried out by Simulated Distillation along with a hydrocarbon types analysis and complemented with CHNS-O analysis and Fourier Transform Infrared Spectroscopy. Two catalytic structures were employed named Sepiolite and Montmorillonites, both K10 and K30, which after simple heat treatment to stabilize the structure, were characterized to analyze the main properties affecting the catalytic activity and product yields (i.e., morphological and acidity properties). A whole screaming of the products by analogy with hydrocarbon of the petroleum industry is presented. Such an approach allows a real evaluation of the studied technology in the current energy scenario