Catalytic Cracking Gas Research Articles

Research and selection of catalysts for the process of alkylation of oil fractions with catalytic cracking gases

The article presents the results of the study and use of modified zeolite-containing catalysts (ZSM-5) and natural alumosilicates (halloisite) in the process of alkylation of distillate fraction with catalytic cracking gases. Based on thermogravimetric analysis, it was determined that modification of halloisite with the Al+CCl4 system leads to the appearance of peaks indicating exo- and endo processes under the influence of temperature. When the oil fraction was alkylated at a temperature of 50 oC on Al+CCl4+halloisite catalyst with catalytic cracking gases containing olefins of 43.47 % the viscosity index was increased from 32 to 84. Based on NMR spectra, it was determined that alkylates differ from the original oil fraction by increased values isoparaffin index, the number of protons in aromatic structures and those furthes from the aromatic nucleus. These data confirm the improvement in the viscosity temperature characteristics of the oil fraction. Alkylation of an oil fraction with a viscosity index of 49.9 on ZSM-5 and ZSM-5-ZrO2 catalysts made it possible to obtain oils with a viscosity index of 80.7 and 137, respectively. Based on X-ray diffraction studies using rentgenographic method, it was shown that Zr is contained in the structure of ZSM-5 zeolite in the form of ZrO2. The introduction of Zr into the crystaline structure of the zeolite helps to increase the activity of the modified catalyst ZSM-5-ZrO2. Research has shown that the phase composition of samples of the modified ZSM-5-ZrO2 zeolite changes depending on the calcination temperature. An increase in temperature from 200 to 550 oC leads to the transition of the amorphous phase to the crystalline phase, and at a given calcination temperature a phase belonging to ZrO2 appears. The introduction of Zr into the catalyst composition leads to a change in the ratio of the Lewis and Brensted acid sites of the ZSM-5 catalyst. Namely, there is an increased Lewis and a decreased Brensted acid sites. Based on this it can be assumed that both Brensted and Lewis acid sites take part in the alkylation process.

NEW COMPONENTS OF LOW-VISCOSITY MARINE FUEL BASED ON LOW-VALUE AND BY-PRODUCTS OF OIL REFINING

A comprehensive study of the hydrocarbon composition and physicochemical properties of by-products of oil refining and petrochemistry was carried out to search for new low-margin components of low-viscosity marine fuel (LMF) and to optimize the fuel composition for expanding the raw material base of LMF. The possibility of involving the heavy fractions from primary and secondary oil refining in LMF has been established: 10-12 % higher-weight diesel fraction, 47-60 % straight-run medium distillate fraction, 2-10 % heavy diesel fraction, 35% vacuum distillate, 10 % still residue from hydrogenation units, 4-10 % light catalytic cracking gas oil. A method has been found for obtaining a new component of LMF - a fraction boiling within 180-270 °C, obtained from oil refining wastes after their dehydration and fractionation in the yield of up to 30 %, the involvement of which in LMF (5 %) will give an economic effect of about 7 million roubles per year. Mathematical modelling was used to optimize the composition of fuel from the main and by-products, taking into account the production volumes and the actual values of critical indicators of each component. A method has been found for obtaining a new component of LMF - a fraction boiling within 180-270 °C, obtained from oil refining wastes after their dehydration and fractionation in the yield of up to 30 %, the involvement of which in LMF (5 %) will give an economic effect of about 7 million roubles per year. Mathematical modelling was used to optimize the composition of fuel from the main and by-products, taking into account the production volumes and the actual values of critical indicators of each component.

ASESSMENT OF THE EFFECTIVENESS OF CAVITATION PROCESSING OF DARK OIL PRODUCTS

The paper presents experimental results of the influence of the conditions of cavitation treatment of dark petroleum products in the hydrodynamic regime on the yield of fractions boiling up to 400 °C. Straight-run products (fuel oils, vacuum gas oils), as well as catalytic cracking gas oils, were considered as raw materials. The influence of raw material characteristics (density, fractional and group hydrocarbon composition) and its processing conditions (pressure, at five cycles of exposure) on the yield of the target fraction is considered. The linear dependence of the yield of the target fractions on the processing pressure is revealed. The constructed regression models are adequate, informative, and all their coefficients are significant. Taking into account the density of the feedstock did not improved models. The best model constructed was tested using the cross-validation method. The average forecast error was 11%, the maximum was 22%. For a small number of samples, such an error is acceptable. The possibility of assessing the effectiveness of cavitation treatment of crude oil based on data on its fractional and group hydrocarbon composition is shown. It was possible to build several regression models linking the increase in yield with pressure during processing and the content of resins and oils in the raw materials. All of them are adequate and informative, and their coefficients are significant. The increase in the yield of fractions boiling up to 400 °C is associated with the transformations of hydrocarbons during cavitation. The possibility of evaluating the effectiveness of cavitation treatment of petroleum raw materials based on data on its group hydrocarbon composition has been established. Several regression models have been constructed linking the increase in yield with the pressure during processing and the content of resins and oils in the raw materials. All of them are adequate and informative, and their coefficients are significant. Based on the constructed models, it is assumed that the change in the fractional composition of petroleum products during cavitation treatment is more associated with the destruction of the transition and solvate layers of complex structural units of the oil dispersed system than with the course of cracking reactions. For citation: Peshnev B.V., Burlyaeva E.V., Nikishin D.V., Nikolaev A.I., Kuznetsov A.S. Asessment of the effectiveness of cavitation processing of dark oil products. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 7. P. 103-110. DOI: 10.6060/ivkkt.20246707.7006.

Improving the viscosity-temperature properties of oil fractions in the process of alkylation with catalytic cracking gases on zeolite-containing catalyst

Improving the viscosity-temperature properties of oil fractions in the process of alkylation with catalytic cracking gases on zeolite-containing catalyst

ЭКСТРАКЦИОННОЕ ДЕАЗОТИРОВАНИЕ И ОБЕССЕРИВАНИЕ СМЕСИ ГАЗОЙЛЕЙ ВИСБРЕКИНГА И КАТАЛИТИЧЕСКОГО КРЕКИНГА N-МЕТИЛПИРРОЛИДОНОМ

There are presented the results of a single-stage extraction of a mixture of visbreaking and catalytic cracking gas oils in a mass ratio of 70 : 30 N-methylpyrrolidone with 2 % of water by weight and extractant-to-raw material ratios of 0.5 : 1, 1 : 1 and 1.5 : 1, as well as two-stage cross-current extraction and four-stage countercurrent extraction with a mass ratio of the extractant to a mixture of gas oils 1 : 1. With four-stage extraction, the sulfur content is reduced 7.5 times to 0.269 % by weight in refined products, which is significantly lower than the permissible level in marine fuel for open water areas

Research and Application of Modified ZSM-5 for the Process of Alkylation of Oil Distillate Fractions

In the oil distillate fraction alkylation process, a modified Zr zeolite ZSM-5 was obtained and studied. The modification was executed using a method that impregnated ZSM-5 with a 5% solution of ZrOCl<sub>2</sub>∙6H<sub>2</sub>O. X-ray diffraction studies were conducted on zeolite ZSM-5, zirconyl chloride modifier ZrOCl<sub>2</sub>∙6H<sub>2</sub>O, and modified zeolite ZSM-5-ZrO<sub>2</sub>, which was calcined at temperatures of 200, 400, and 550°C. The results revealed that the phase composition of modified ZSM-5-ZrO<sub>2</sub> zeolite samples varied depending on the calcination temperature. It was determined that only at a temperature of 550°C did the modified ZSM-5 catalyst contain three phases belonging to ZrSi<sub>24</sub>O<sub>50</sub>, ZrO<sub>2</sub>, and ZSM-5. The emergence of the ZrO<sub>2</sub> phase occurred at a calcination temperature of 550°C. An increase in temperature from 200 to 550°C facilitated the transition of the amorphous phase to the crystalline phase. The crystal structure of the ZSM-5-ZrO<sub>2</sub> catalyst, calcined at 550°C, contributed to a rise in its activity. Consequently, during alkylation with catalytic cracking gases, the viscosity-temperature properties of the T-30 turbine oil distillate fraction significantly improved (the viscosity index increased from 49.9 to 137). An increase in zeolite ZSM-5 activity was demonstratd due to the introduction of zirconium and an elevated calcination temperature to 550°C.

ЭКСТРАКЦИОННАЯ ОЧИСТКА ЛЕГКОГО ГАЗОЙЛЯ КАТАЛИТИЧЕСКОГО КРЕКИНГА ОТ ГЕТЕРОАТОМНЫХ КОМПОНЕНТОВ И ПОЛИАРОМАТИЧЕСКИХ УГЛЕВОДОРОДОВ СМЕСЯМИ N-МЕТИЛПИРРОЛИДОН – ЭТИЛЕНГЛИКОЛЬ

The results of single-stage, as well as two- and three-stage cross-current extraction of sulfurous and nitrogenous components, aromatic and unsaturated hydrocarbons from light catalytic cracking gas oil with mixtures of N-methylpyrrolidone with ethylene glycol composition 80/20, 70/30 and 60/40 wt. % are presented with a mass ratio of extragent : raw materials 1 : 1 and a temperature of 40 оC. The degree of extraction of sulfur compounds at the ethylene glycol content in the extractant is 30 wt. % as a result of single-stage extraction is 70 %, and with three-stage purification - about 90 %, the cetane index of raffinate increases by more than 13 and 19 points, respectively

Кинетические особенности термолиза газойлей каталитического крекинга

The high-temperature macrokinetics of the process of thermolysis of low-sulphur catalytic cracking gas oil with the formation of needle coke was studied. The experiments were carried out on a laboratory setup with a quartz microreactor at temperatures of 450-500 °C and a process duration of up to 300 min. It was established that the process is two-stage and its kinetics obeysthe Avrami-Erofeev equation, the rate constant of the process at both stages has a diffusion character. The second stage includes thermal condensation of polycyclic hydrocarbons with the formation of mesophase and needle coke. The results of the study are confirmed by optical microscopy in polarized light, data of electron paramagnetic resonance and electron spectroscopy.

Оценка возможности получения мезофазы при термообработке различных видов углеводородного сырья

The possibility of obtaining anisotropic pitches by heat treatment of various types of petroleum feedstock is shown - isotropic pitches from heavy pyrolysis tar and heavy catalytic cracking gas oil. The dependences of the change in the group compositionof the heat treatment residues on the duration of isothermal exposure, the correlation between the components insoluble in toluene and quinoline, have been established. Features of the optical texture of the heat treatment residues of isotropic petroleum pitches of various origins are revealed.

Hydrodynamic activation of heavy oil residues

Objectives. Recently, there has been a tendency to increase the volume of high-viscosity heavy oils in the total volume of oil produced. The processing of these oils requires new technological approaches. This task is closely related to the need to increase the depth of oil refining. Among the approaches proposed to solve these problems, mechanochemical activation, which is based on the cavitation effect produced by ultrasonic or hydrodynamic methods, has been suggested. This study evaluated the effects of cavitation in increasing the depth of oil refining.Methods. Straight-run and “secondary” oil products were used as raw materials: vacuum gas oil, catalytic cracking gas oil, and fuel oil. Activation was carried out in a high-pressure disintegrator. The principle of operation was to compress the oil product and then pass it through a diffuser. When the oil was passed through the diffuser, there was a sharp pressure release to atmospheric pressure, which caused cavitation in the hydrodynamic flow. The pressure gradient on the diffuser and the number of processing cycles ranged from 20 to 50 MPa and 1 to 10, respectively. The density, refractive index, and the fractional composition of petroleum products were determined using standard and generally accepted methods.Results. This paper reports the influence of mechanochemical activation of petroleum products on their physical and chemical characteristics. An increase in the pressure gradient and the number of processing cycles leads to a decrease in the boiling point of the petroleum products and their density and an increase in the yield of fractions that boil off below 400 °C. The yield of the fractions with boiling points of 400–480 °C and the remainder were reduced. The density and refractive index of fractions with boiling points up to 480 °C decreased, and the density of the residue increased. The effects of cavitation (an increase in the yield of fractions with boiling points up to 400 °C and a decrease in the density of the petroleum products) increased with increasing pressure gradient and the number of processing cycles.Conclusions. The changes in the density, boiling point, and the yield of fractions increased with increasing the pressure from 20 to 50 MPa and the number of hydrodynamic cavitation cycles from 1 to 5. Increasing the number of processing cycles to more than five had little additional effect. The effects of cavitation increased with increasing initial density of the oil product. The average molecular weight of these fractions was estimated from the densities and boiling points of individual fractions of the petroleum products. The calculation confirmed the assumption regarding the course of cracking reactions of petroleum products under the influence of cavitation and indicates the course of the compaction processes.

Mapping technique for oil refining processes and products

The technique is proposed for visualizing the product compositions and the refractodenses (trajectories) of oil refinery processes, based on measuring the refractive index and density of the liquid product flows of operating procedures, computing the specific refraction and refraction intercept, and constructing a Kurtz-Lorentz identification map, the center of which is the “polymethylene center”. Trajectories-refractodenses of the processes of atmospheric-vacuum distillation of oil, catalytic reforming, hydrocracking of vacuum and heavy gas oil, products of secondary oil refining (motor gasoline, diesel fuel, catalytic cracking gasoline, light catalytic cracking gas oil) and their fractional distillation have been constructed. An express method is also proposed for evaluating the group hydrocarbon compositions of straight-run oil fractions, upon which we propose a three-digit composition marking of straight-run fractions. It is shown that the logarithms of isomeric alkanes contents in straight-run oil fractions are linearly correlated with their molar enthalpies of vaporization.

Transformation of Paraffin and Olefin Hydrocarbons on a Modified Zeolite-Containing Catalyst of Cracking

Industrial zeolite-containing OMNIKAT-210P catalyst modified with Ni, Co, Cr is used as a catalyst to study the conversion of hydrocarbons contained in catalytic cracking gases. The aim of the study is to obtain a high-octane component of gasoline. The metals are deposited on nanosized particles of a zeolite-containing catalyst. The particle size is at a level of (5–10) × 10−9 m. The particle size allows metals Ni, Cr, Co to be applied evenly on the surfaces of the nanoparticles. The particles then form balls 2–3 mm in size that are dried (120°C) and calcined (450–500°C). The yield of liquid products is at a level of 48.3–30.3 wt %, depending on the time of sampling.

Transformation of paraffin and olefin hydrocarbons on the modified on the zeolite-containing cracking catalyst

As a catalyst for studying the conversion of hydrocarbons contained in catalytic cracking gases, a modified Ni, Co, Cr industrial OMNIKAT-210P zeolite-containing catalyst was used. The purpose of the research is to obtain a high-octane component of gasoline. The deposition of metals was carried out on nano-sized particles of a zeolite-containing catalyst. Particle size was at the level of (5÷10)·10–9m. The particle size allows you to evenly apply the metals Ni, Cr, Co on the surface of the nanoparticles. Then the particles are molded in the form of balls with a size of 2–3 mm and subjected to drying (120 °С) and calcining 450–500 °С. The yield of liquid products is at the level of 48.3–30.3 % of the mass.

A Study of the Products of Alkylation of Turbine Oil Distillate with Catalytic Cracking Gases

The main physicochemical properties and structural parameters of the products of alkylation of the turbine oil distillate with catalytic cracking gases on Zeokar-600 and Omnikat-210P zeolite catalysts have been determined using IR, 1H NMR, and UV spectroscopy techniques. Alkylation has been carried out in the temperature range of 50–150°C at oil : gas ratios of 1 : 1 and 1 : 2. The reaction products have been studied. The products have been obtained under optimal conditions, ensuring the maximum increase in the viscosity index of the oil fraction from 32 to 75 and 53 on the Zeokar-600 and Omnikat-210P catalysts, respectively. It has been shown that the kinematic viscosity and viscosity index of the oil fraction are increased by the alkylation. This is due to an increase in the length and quantity of alkyl substituents of aromatic hydrocarbons by adding propylene and butylene units of olefin hydrocarbon gases of catalytic cracking.

Experimental Study on Spent FCC Catalysts for the Catalytic Cracking Process of Waste Tires

Research on the synergistic high-value reuse of waste tires and used catalysts in spent fluid catalytic cracking (FCC) catalysts was carried out in this study to address the serious ecological and environmental problems caused by waste tires and spent FCC catalysts. The experiment, in which a spent FCC catalyst was applied to the catalytic cracking of waste tires, fully utilized the residual activity of the spent FCC catalyst and was compared with a waste tire pyrolysis experiment. The comparative experimental results indicated that the spent FCC catalyst could improve the cracking efficiency of waste tires, increase the output of light oil in pyrolysis products, and improve the quality of pyrolysis oil. It could also be used for the conversion of sulfur compounds during cracking. The content of 2-methyl-1-propylene in catalytic cracking gas was found to be up to 65.59%, so a new method for producing high-value chemical raw materials by the catalytic cracking of waste tires with spent FCC catalysts is proposed.

Catalytic Activity of an Al—CI—Re System for n-Hexane Cracking

End products of n-hexane cracking in a displacement fixed-bed catalytic reactor (Pt + Re + In + Ti)/γ-Al2O3 with specific surface area 193 m2/g were investigated. The catalytic system was crystalline γ -Al2O3 with lattice constants 8 A and average crystallite size 4.8 nm. The degree of conversion of n-hexane doubled and the selectivity for methyl-substituted benzene increased by 33.2% as the temperature was increased from 400 to 450°C. The amount of carbonaceous reaction products was unaffected by the increased process temperature although the yield of gaseous products increased significantly. The isobutane content in n-hexane catalytic cracking gases exceeded 30 vol.%. The elemental and phase compositions of the catalytic system did not change during the experiment.

Dimerization of Isobutene in C4 Mixtures in the Presence of Ethanol Over Acid Ion-Exchange Resin DH-2

Isobutene dimerization of C4 mixtures with the simulated components of industrial fluid catalytic cracking (FCC) gas stream was carried out in a fixed-bed microreactor over the acid ion-exchange resin (DH-2) in the presence of ethanol. The influences of ethanol/isobutene molar ratio and reaction temperature on the isobutene dimerization reaction were studied. For 1-butene, both isomerization and oligomerization simultaneously take place, but the isomerization reaction is more sensitive to reaction temperature than oligomerization. And both reactions were inhibited noticeably in the presence of ethanol. Although the conversion of isobutene was reduced to some extent when ethanol was introduced, it was beneficial for improving the weight fraction of dimers in oligomers as well as trimethylpentenes in dimers. With ethanol addition, the dimerization reaction was less sensitive to the reaction temperature thus the isobutene dimerization reaction can be performed in a wide temperature range.

Process of Alkylating of Oily Fractions with Catalytic Cracking Gases

Process of Alkylating of Oily Fractions with Catalytic Cracking Gases

REGULATION OF POLYMER-BITUMEN BINDERS PROPERTIES BY COMPOSITION PLASTIFICATOR SELECTION

Background The durability of motor roads is affected by the physical, chemical and operational properties of bitumen. Modification of bitumen is a promising method for improving the properties of binders. The polymeric modifier allows to significantly improve the physical, chemical and operational properties of bitumen. Plasticizers are used to regulate the group chemical composition and the structure of the bituminous binder in the technology for the production of polymer-bituminous binders (PBB). As a plasticizer, industrial oil is often used. However, it has a high cost and is not effective enough in the production of PBB. Aims and Objectives The aims of the work are the development of a combined plasticizer on the basis of by-products of oil refining for the production of PBB, the cost of which is commensurate with the cost of raw bitumen production, and also the study of the influence of the composition of the combined plasticizer on the physicochemical properties of the bitumen binder. To produce the combined plasticizer, a heavy catalytic cracking gas oil rich in arene hydrocarbons and promoting the swelling of the polymer was used, and a vacuum gas oil that imparts elastic-plastic properties to the material. Polymer-bitumen binders were obtained on the basis of bitumen of BND 60/90 and thermoplastic elastomer DST-30-01. Results It has been established that the softening temperature of the PBB samples with an increase in the content of vacuum gas oil in the combined plasticizer remains practically unchanged, the adhesion index has the minimum values with the composition of the combined plasticizer of 50:50 and with an increase in the polymer content in the PBB it also decreases. With the increase in the content of DST-30-01 in bitumen, hardening of the structure is observed, and the change in the softening temperature after aging decreases. As the polymer content in the bitumen increases and the ratio of the plasticizer components is 50:50 and 30:70, the produced PBB have increased values of the maximum tensile strength or cohesive strength and can ensure the creation of durable road surface. Analysis of the results of the research shows that the change in the operating parameters of the PBB is achieved through the regulation of its group chemical composition by a combined plasticizer. With a certain composition of the combined plasticizer, it is possible to achieve the necessary physic-mechanical parameters of the PBB. Also, the use of by-products of oil refining in the combined plasticizer will reduce the cost of polymer-bitumen materials.

Experimental Study on the Integrated Performance of Dust Removal and Water Vapour Recovery in Catalytic Cracking Gas

Industrial combustion flue gas contains fine dust, water vapor, in order to remove micro dust, and to recover water vapor at the same time. we have put forward a research on the technology of recovering water vapor and dust removal by using a cyclone separator for the first time. By studying the pressure drop, the separation efficiency and the efficiency of recovering condensed water of the flue gas, we can get the optimum technological parameters for the actual working conditions. The results show that the pressure drop increases with the increase of inlet velocity and temperature, and the rate of increase is increasing. When under the same cooling water flow rate, the dust separation efficiency increases first and then decrease with the inlet velocity increase. When the inlet velocity is near the 50 m3/h, the separation efficiency reaches the maximum, 96%. The amount of vapor recovery increases with the increase of cooling medium flow rate in 15 minutes. When at the same cooling medium flow rate, the recovery increases first and then decrease with the inlet velocity increase, and reaches the maximum when the inlet velocity is 60-80 m3/h.