Thermocracking of a heavy fraction of the oil residue in a mixture with shale

The process of tar thermal cracking in a mixture with crushed oil shale to obtain components of motor fuels and raw materials for the process of thermal cracking is investigated in this paper. The optimization results of technological parameters (shale concentration, temperature, and duration) are presented and the material balance (mass.%) of the process is made. It was found that during single-stage processing under relatively mild conditions (5 MPa, 425C, feed space velocity of 1.0 h-1), a deep destruction of tar is achieved (the yield of the gasoline fraction from boiling point to 200C is ~12 wt.%; medium distillates with boil. point 200370C-43-44 mass.%; raw materials for thermal cracking with boil. point above 370C ~15-16 wt.% on per the original tar). The generating coke-like products and the V and Ni contained in the raw materials are deposited on the mineral part of the shale and removed from the reaction zone with the liquid products of the process.

Effect of Acid Treatment on the Properties of Zeolite Catalyst for Straight-Run Gasoline Upgrading

The objective of this research was to analyze the effect of different concentrations of nitric and hydrochloric acids on the structural, acidic, and catalytic properties of a post-synthetic treated ZSM-5 type zeolite at various temperatures. The properties of zeolite catalysts were determined using different methods, such as the Brunauer-Emmett-Teller (BET) method for specific surface area, temperature-programmed desorption (TPD) of ammonia method for acidic properties, and a flow-through unit with fixed bed catalyst (with upgrading straight-run gasoline fraction of oil) for catalytic activities of initial zeolite and acid-treated samples. The structural and acidic properties of both untreated and treated zeolites were investigated, and the effect of acid treatment on the catalytic properties of the samples in the course of upgrading the straight-run gasoline fraction of oil was determined. The post-synthetic treatment with aqueous nitric acid increased the specific surface area and volume of micropores of ZSM-5 zeolite, while the treatment with aqueous hydrochloric acid led to the formation of mesopores. Acid treatments of zeolite decreased the number of acid sites, mainly due to diminished concentration of low-temperature sites. The yield of liquid products in the conversion of straight-run gasoline fraction of oil, i.e., generation of high-octane gasolines with improved environmental features, was increased using acid-treated zeolites, which was due to the decrease in arene content.

Synthesis of Nickel-loaded Sulfated Zirconia Catalyst and Its Application for Converting Used Palm Cooking Oil to Gasoline via Hydrocracking Process

The synthesis of the nickel-loaded sulfated zirconia catalyst (Ni-SZ) and its application for the hydrocracking process have been carried out. This work has been conducted to determine the activity and selectivity from various Ni concentrations loaded on sulfated zirconia (SZ) in the hydrocracking of used palm cooking oil. The synthesis technique was preceded by sulfation of ZrO2 through incipient wetness impregnation method using H2SO4 solution and then continued with the impregnation of Ni via hydrothermal method employing NiSO4 · 6H2O precursor salt. The hydrocracking process was performed in a fix-bed microreactor at the optimum temperature (350 °C). The SZ loaded with 3 wt% of Ni (Ni-SZ 3) successfully produced the highest liquid product (44.25 wt%) and selectivity on gasoline (100 %). Besides, the gasoline fraction in the liquid product was dominated by unwanted aromatics compounds. The excellent performance of Ni-SZ 3 due to it has high acidity value, specific surface area, and Ni content.

Catalytic Hydrocracking of Fresh and Waste Frying Oil over Ni- and Mo-Based Catalysts Supported on Sulfated Silica for Biogasoline Production

The synthesis of a sulfated silica catalyst and its modification with Ni and/or Mo metal, along with its application for the hydrocracking of fresh and waste frying oil into biogasoline, were conducted. Synthesis of the catalysts was initiated with the sulfation of silica (SiO2) material by H2SO4 using the sol-gel method. Ni and/or Mo metal were impregnated into the SO4/SiO2 matrix with concentration variations of 1, 2, and 3 wt%. The sulfation process and promotion by Molybdenum (Mo) metal in the modified catalyst successfully increased the catalytic activity and selectivity. Among the catalysts investigated, Ni-SS2 exhibited the best performance for the hydrocracking reaction with waste frying oil. This catalyst was able to achieve a conversion of the liquid product of 71.47% and a selectivity of 58.73% for the gasoline fraction (C5-C12). NiMo-SS3 showed the highest percentage of activity and selectivity in the hydrocracking of fresh frying oil at 51.50 and 43.22 wt%, respectively.

Performance of Ni-Mo Sulfated Nanozirconia Catalyst for Conversion of Waste Cooking Oil into Biofuel via Hydrocracking Process

The synthesis of the Ni-Mo sulfated zirconia (NiMo-SZ) catalyst and its application to convert waste cooking oil into biofuel was successfully conducted. The synthesis process was started with a sulfation process on the zirconia oxide (ZrO2) using 0.5, 1.0, and 1.5 M sulfuric acid (H2SO4) through wet impregnation to obtain sulfated zirconia (SZ). Solid SZ with the highest total acidity value was calcined at temperature 500, 550, 600, 650, and 700 °C. Solid SZ calcined with the optimum temperature was treated with Ni and Mo metals at 1%, 2%, and 3% (w/w) through a hydrothermal method. Pure ZrO2, SZ, and 1, 2, and 3 NiMo-SZ catalysts were used in the hydrocracking of used cooking oil into biofuel. The results showed that the 1.5 M SZ catalyst calcined at 500 °C had the highest acidity value of 3.8137 mmol/g. The 3-NiMo-SZ catalyst had the best activity valuing at 80.54%, while 1-NiMo-SZ produced the best selectivity in producing gasoline fraction until 73.93%.

Physicochemical and Catalytic Properties of Rhenium-Containing Zeolites in the Course of Straight-Run Gasoline Upgrading

Catalysts for upgrading of the straight-run gasoline fraction of oil were prepared on the basis of a ZSM‑5 zeolite via dry mechanical mixing with an ultrafine rhenium powder. It was shown how the structural and acidic characteristics of zeolite ZSM‑5 changed when it was modified with rhenium. The concentration and nature of carbon condensation products formed on the prepared catalysts during the processing of straight--run gasoline have been determined. An enhancement of operating efficiency of rhenium--containing zeolite catalysts in comparison with an unmodified zeolite was established, which consisted in increasing their capacity and reducing the rate of deactivation in the process under study

Increasing the Yield of Light Distillates by Wave Action on Oil Raw Materials

The article presents the results of the electromagnetic activation of petroleum feed in the vortex layer apparatus. It is shown that under the electromagnetic influence, there is a significant increase in the proportion of straight-run gasoline fraction distillate, as well as a change in the physicochemical parameters of the light fractions obtained as a result of the cavitation effect and the low-temperature cracking. It has been established that the processes of wave action on oil occurring in the electromagnetic field zone lead to a change in the individual and group hydrocarbon composition of the distillates obtained. The gasoline fraction produced from activated petroleum, due to an increase in the proportion of aromatic compounds, has a high octane number compared to the original straight-run fraction and low content of alkenes, which allows us to recommend its use as a high-octane component of motor fuels in the compounding and production of commercial gasoline.

Reactivation of the Spent Residue Fluid Catalytic Cracking (RFCC) Catalyst through Acid Treatment for Palm Oil Cracking to Biofuels

This work discusses the treated spent Residue Fluid Catalytic Cracking (RFCC) catalysts using sulfuric or citric acids to examine the impact of acid treatment on the catalyst physicochemical properties and structural characteristics. The catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), and Brunauer−Emmett−Teller-Barrett−Joyner−Halenda (BET-BJH) methods. The catalytsts were performed in a continuous fixed-bed reactor for catalytic cracking of palm oil. Changes of the catalyst characteristics and catalytic performance testing of the catalyst after the acid treatment for palm oil cracking process were discussed. It was found that the acid treatment on the spent RFCC catalyst can increase the surface area and pore volume of catalysts as well as the crystallinity. The closed pores in the spent RFCC are opened by acid treatment by eliminating heavy metals. Concerning to the catalytic performance, the acid-treated catalysts had better performance than the non-treated catalyst, which could increase selectivity of the kerosene-diesel range fraction from 47.89% to 55.41%. It was interested, since the non-treated catalyst could not produce gasoline fraction, while the acid-treated catalsysts could produce gasoline fraction at selectivity range of 0.57 – 0.84%. It was suggested that both sulfuric or citric acids treatment could increase the cracking performance of spent RFCC catalyst by shifting the product to lower hydrocarbons.

Modeling the properties of Kukersite shale gasoline

Based on new experimental data for Kukersite shale oil, it is now possible to develop a property prediction model for the gasoline fraction of shale oil. Such a model was created based on estimation of the composition along with experimental boiling point and density data. First, correlations were developed to estimate the composition of a Kukersite shale gasoline sample based on the boiling point and density of narrow fractions. The estimated composition was then used with the PC-SAFT equation of state to calculate the properties of shale gasoline. To do so, correlations were developed to predict the PC-SAFT parameters of the various classes of compounds present in Kukersite shale gasoline. The utility of this model was shown by predicting the vapor pressure of various portions of the shale gasoline.

Virtual Soft Sensor of the Feedstock Composition of the Catalytic Reforming Unit

The paper discusses a method for obtaining a matrix of individual and group composition of a hydrotreated heavy gasoline fraction in industrial conditions based on the fractional composition obtained by the distillation method according to the ASTM D86 (the Russian analogue of such a standard is GOST 2177). A method for bounds estimation of the retention index (RI) change is considered on the basis of the symmetry of the RI change range relative to its arithmetic mean. Implementation of this method is performed by simulation of individual composition of C6–C12 feedstock of the catalytic reforming unit in the software package. For this purpose, the boiling curve of individual composition of hydrocarbon mixture is converted into the corresponding curve of fractional composition. The presented technique of creating a virtual soft sensor makes it possible to establish a correct relationship between the fractional composition and the individual hydrocarbon composition obtained according to the IFP 9301 (GOST R 52714) (Russian GOST R 52714 and international IFP 9301 standards for the determination of individual and group composition of hydrocarbon mixtures by capillary gas chromatography). The virtual soft sensor is based on chemical and mathematical principles. The application of this technique on the data of a real oil refinery is shown. Obtaining accurate data by means of a virtual soft sensor on the individual composition of feedstock will make it possible to optimize the catalytic reforming process and thus indirectly improve its environmental friendliness and enrichment efficiency.