Browsing by Author "Yordanov D."
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Item Alternative Options for Ebullated Bed Vacuum Residue Hydrocracker Naphtha Utilization(2023-12-01) Stratiev D.; Shishkova I.; Ivanov M.; Dinkov R.; Toteva V.; Angelova D.; Kolev I.; Tavlieva M.; Yordanov D.The vacuum residue hydrocracker naphtha (VRHN) is a chemically unstable product that during storage changes its colour and forms sediments after two weeks. It cannot be directly exported from the refinery without improving its chemical stability. In this research, the hydrotreatment of H-Oil naphtha with straight run naphtha in a commercial hydrotreater, its co-processing with fluid catalytic cracking (FCC) gasoline in a commercial Prime-G+ post-treater, and its co-processing with vacuum gas oil (VGO) in a commercial FCC unit were discussed. The hydrotreatment improves the chemical stability of H-Oil naphtha and reduces its sulphur content to 3 ppm. The Prime-G+ co-hydrotreating increases the H-Oil naphtha blending research octane number (RON) by 6 points and motor octane number (MON) by 9 points. The FCC co-cracking with VGO enhances the blending RON by 11.5 points and blending MON by 17.6 points. H-Oil naphtha conversion to gaseous products (C1–C4 hydrocarbons) in the commercial FCC unit was found to be 50%. The use of ZSM 5 containing catalyst additive during processing H-Oil naphtha showed to lead to FCC gasoline blending octane enhancement by 2 points. This enabled an increment of low octane number naphtha in the commodity premium near zero sulphur automotive gasoline by 2.4 vol.% and substantial improvement of refinery margin. The processing of H-Oil naphtha in the FCC unit leads also to energy saving as a result of an equivalent lift steam substitution in the FCC riser.Item Chercher de l'eau: The switching mechanism of the rotary switch ethyl-2-(2-(quinolin-8-yl)hydrazono)-2-(pyridin-2-yl)acetate(2020-05-01) Deneva V.; Vassilev N.; Hristova S.; Yordanov D.; Hayashi Y.; Kawauchi S.; Fennel F.; Völzer T.; Lochbrunner S.; Antonov L.The E/Z switching mechanism of the rotary switch ethyl-2-(2-(quinolin-8-yl)hydrazono)-2-(pyridin-2-yl)acetate was studied by NMR, UV–Vis, and ultrafast spectroscopy and modeled by advanced quantum-chemical calculations. Three possible mechanisms were considered theoretically: out-of-plane rotation, in-plane inversion and proton transfer. Neither of them correctly describes the experimental data by using implicit solvation. Taking into account the existence of water in the used solvents, which influence the measured rate constants, an explicit solvation was attempted in the quantum-chemical calculations. According to a simplified model, the water molecules form a wire, being able to transfer the proton from Z to E form of the switch. This leads to substantially lower transition states and corresponds to the experimentally observed rate constants. This information shines new light on the mechanism of isomerization in the rotary switches and on the understanding of the mechanism of hydrazone tautomerism as a whole.Item Commercial Investigation of the Ebullated-Bed Vacuum Residue Hydrocracking in the Conversion Range of 55-93%(2020-12-29) Stratiev D.; Nenov S.; Shishkova I.; Georgiev B.; Argirov G.; Dinkov R.; Yordanov D.; Atanassova V.; Vassilev P.; Atanassov K.The LUKOIL Neftohim Burgas vacuum residue hydrocracking has increased the vacuum residue conversion from 55 to 93% as a result of a proper feed selection, optimal catalyst condition, and the use of a Mo nanodispersed catalyst. It was found that the feed colloidal instability index estimated from the feed saturates, aromatics, resins, and asphaltenes (SARA) data negatively correlated with the conversion. Correlations based on the use of the nonlinear least-squares method, which relates the density to the aromatic structure contents for the straight run and hydrocracked vacuum residues, were developed. Intercriteria analysis was applied to evaluate the relations between the different properties of the straight run and the hydrocracked vacuum residual oils. The density of the hydrocracked vacuum residue measured by dilution with toluene was found to strongly correlate with the conversion, Conradson carbon content, softening point, and Fraasss breaking point.Item Comparison of empirical models to predict viscosity of secondary vacuum gas oils(2021-08-01) Stratiev D.S.; Nenov S.; Shishkova I.K.; Dinkov R.K.; Zlatanov K.; Yordanov D.; Sotirov S.; Sotirova E.; Atanassova V.; Atanassov K.; Stratiev D.D.; Todorova‐yankova L.This work presents characterization data and viscosity of 34 secondary vacuum gas oils (H‐Oil gas oils, visbreaker gas oils, and fluid catalytic cracking slurry oils) with aromatic content reaching up to 100 wt.%. Inter‐criteria analysis was employed to define the secondary VGO charac-teristic parameters which have an effect on viscosity. Seven published empirical models to predict viscosity of the secondary vacuum gas oils were examined for their prediction ability. The empirical model of Aboul‐Seud and Moharam was found to have the lowest error of prediction. A modifica-tion of Aboul‐Seoud and Moharam model by separating the power terms accounting for the effects of specific gravity and average boiling point improves the accuracy of viscosity prediction. It was discovered that the relation of slope of viscosity decrease with temperature enhancement for the secondary vacuum gas oil is not a constant. This slope increases with the average boiling point and the specific gravity augmentation, a fact that has not been discussed before.Item Crude slate, FCC slurry oil, recycle, and operating conditions effects on H-Oil® product quality(2021-06-01) Stratiev D.S.; Shishkova I.K.; Dinkov R.K.; Petrov I.P.; Kolev I.V.; Yordanov D.; Sotirov S.; Sotirova E.N.; Atanassova V.K.; Ribagin S.; Atanassov K.T.; Stratiev D.D.; Nenov S.This paper evaluates the influence of crude oil (vacuum residue) properties, the processing of fluid catalytic cracking slurry oil, and recycle of hydrocracked vacuum residue diluted with fluid catalytic cracking heavy cycle oil, and the operating conditions of the H-Oil vacuum residue hydroc-racking on the quality of the H-Oil liquid products. 36 cases of operation of a commercial H-Oil® ebullated bed hydrocracker were studied at different feed composition, and different operating con-ditions. Intercriteria analysis was employed to define the statistically meaningful relations between 135 parameters including operating conditions, feed and products characteristics. Correlations and regression equations which related the H-Oil® mixed feed quality and the operating conditions (reaction temperature, and reaction time (throughput)) to the liquid H-Oil® products quality were developed. The developed equations can be used to find the optimal performance of the whole refinery considering that the H-Oil liquid products are part of the feed for the units: fluid catalytic cracking, hydrotreating, road pavement bitumen, and blending.Item Different nonlinear regression techniques and sensitivity analysis as tools to optimize oil viscosity modeling(2021-10-01) Stratiev D.; Nenov S.; Nedanovski D.; Shishkova I.; Dinkov R.; Stratiev D.D.; Stratiev D.D.; Sotirov S.; Sotirova E.; Atanassova V.; Atanassov K.; Yordanov D.; Angelova N.A.; Ribagin S.; Todorova-Yankova L.Four nonlinear regression techniques were explored to model gas oil viscosity on the base of Walther’s empirical equation. With the initial database of 41 primary and secondary vacuum gas oils, four models were developed with a comparable accuracy of viscosity calculation. The Akaike information criterion and Bayesian information criterion selected the least square relative errors (LSRE) model as the best one. The sensitivity analysis with respect to the given data also revealed that the LSRE model is the most stable one with the lowest values of standard deviations of derivatives. Verification of the gas oil viscosity prediction ability was carried out with another set of 43 gas oils showing remarkably better accuracy with the LSRE model. The LSRE was also found to predict better viscosity for the 43 test gas oils relative to the Aboul Seoud and Moharam model and the Kotzakoulakis and George.Item EFFECT OF COMMERCIAL ADDITIVES TO REDUCE SEDIMENT FORMATION IN THE EBULLATED BED VACUUM RESIDUE H-OIL HYDROCRACKING(2020-01-01) Toteva V.; Stratiev D.; Shishkova I.; Nikolaychuk E.; Stanulov K.; Yordanov D.Ten H-Oil residual oils and eleven commercial additives inhibiting the asphaltene agglomeration were explored in this work by employing two tests: hot filtration test (HFT) and asphaltene dispersant test (ADT). It was found that the tendency to form sediments from the asphaltenes in the H-Oil residual oils was different for the distinct feed blends processed in the LNB H-Oil vacuum residue hydrocracker. The performance of the additives was found to be specific to the alloyed H-Oil residual oils. The additive based on the polyisobuthylene succinimide was found to be capable of reducing the sediment content in the H-Oil residual oils produced from all feedstock blends studied in this work. The efficiency of its performance however was different for the studied residual oils being the highest for the residual oil obtained from the feedstock blend 70 % Urals/30 % El Bouri (with the highest tendency to form sediment). This additive has also good efficiency against the H-Oil residual oil obtained from the feed 100 % Urals (with lower tendency to form sediment) but diluted with the high aromatic heavy cycle oil from fluid catalytic cracking.Item Empirical Modeling of Viscosities and Softening Points of Straight-Run Vacuum Residues from Different Origins and of Hydrocracked Unconverted Vacuum Residues Obtained in Different Conversions(2022-03-01) Stratiev D.; Nenov S.; Nedanovski D.; Shishkova I.; Dinkov R.; Stratiev D.D.; Stratiev D.D.; Sotirov S.; Sotirova E.; Atanassova V.; Ribagin S.; Atanassov K.; Yordanov D.; Angelova N.A.; Todorova-Yankova L.The use of hydrocracked and straight-run vacuum residues in the production of road pavement bitumen requires a good understanding of how the viscosity and softening point can be modeled and controlled. Scientific reports on modeling of these rheological properties for hydroc-racked and straight-run vacuum residues are scarce. For that reason, 30 straight-run vacuum residues and 33 hydrocracked vacuum residues obtained in a conversion range of 55–93% were investigated, and the characterization data were employed for modeling purposes. An intercriteria analysis was applied to investigate the statistically meaningful relations between the studied vacuum residue properties. It revealed that the straight-run and hydrocracked vacuum residues were completely different, and therefore their viscosity and softening point should be separately modeled. Through the use of nonlinear regression by applying CAS Maple and NLPSolve with the modified Newton iterative method and the vacuum residue bulk properties the viscosity and softening point were modeled. It was found that the straight-run vacuum residue viscosity was best modeled from the molecular weight and specific gravity, whereas the softening point was found to be best modeled from the molecular weight and C7-asphaltene content. The hydrocracked vacuum residue viscosity and softening point were modeled from a single property: the Conradson carbon content. The vacuum residue viscosity models developed in this work were found to allow prediction of the asphaltene content from the molecular weight and specific gravity with an average absolute relative error of 20.9%, which was lower of that of the model of Samie and Mortaheb (Fuel. 2021, 305, 121609)—32.6%.Item Empirical models to characterize the structural and physiochemical properties of vacuum gas oils with different saturate contents(2021-07-01) Stratiev D.S.; Shishkova I.K.; Dinkov R.K.; Petrov I.P.; Kolev I.V.; Yordanov D.; Sotirov S.; Sotirova E.; Atanassova V.; Ribagin S.; Atanassov K.; Stratiev D.D.; Nenov S.; Todorova‐yankova L.; Zlatanov K.Inter‐criteria analysis was employed in VGO samples having a saturate content between 0.8 and 93.1 wt.% to define the statistically significant relations between physicochemical properties, empirical structural models and vacuum gas oil compositional information. The use of a logistic function and employment of a non‐linear least squares method along with the aromatic ring index allowed for our newly developed correlation to accurately predict the saturate content of VGOs. The empirical models developed in this study can be used not only for obtaining the valuable structural information necessary to predict the behavior of VGOs in the conversion processes but can also be utilized to detect incorrectly performed SARA analyses. This work confirms the possibility of predicting the contents of VGO compounds from physicochemical properties and empirical models.Item Evaluation of the different compatibility indices to model and predict oil colloidal stability and its relation to crude oil desalting(2021-08-01) Shishkova I.K.; Stratiev D.S.; Tavlieva M.P.; Dinkov R.K.; Yordanov D.; Sotirov S.; Sotirova E.; Atanassova V.; Ribagin S.; Atanassov K.; Stratiev D.D.; Todorova-Yankova L.; Nenov S.Thirty crude oils, belonging to light, medium, heavy, and extra heavy, light sulfur, and high sulfur have been characterized and compatibility indices defined. Nine crude oil compatibility indices have been employed to evaluate the compatibility of crude blends from the thirty individual crude oils. Intercriteria analysis revealed the relations between the different compatibility indices, and the different petroleum properties. Tetra-plot was employed to model crude blend compatibility. The ratio of solubility blending number to insolubility number was found to best describe the desalting efficiency, and therefore could be considered as the compatible index that best models the crude oil blend compatibility. Density of crude oil and the n-heptane dilution test seem to be sufficient to model, and predict the compatibility of crude blends.Item Indirect solvent assisted tautomerism in 4-substituted phthalimide 2-hydroxy-Schiff bases(2020-08-15) Yordanov D.; Deneva V.; Georgiev A.; Crochet A.; Fromm K.M.; Antonov L.The paper presents the synthesis and characterization of two 4-substituted phthalimide 2-hydroxy-Schiff bases containing salicylic (4) and 2-hydroxy-1-naphthyl (5) moieties. The structural differences of 2-hydroxyaryl substituents, resulting in different enol/keto tautomeric behaviour, depending on the solvent environment were studied by absorption UV–Vis spectroscopy. Compound 5 is characterized by a solvent-dependent tautomeric equilibrium (KT in toluene = 0.12, acetonitrile = 0.22 and MeOH = 0.63) while no tautomerism is observed in 4. Ground state theoretical DFT calculations by using continuum solvation in MeOH indicate an energy barrier between enol/keto tautomer 5.6 kcal mol−1 of 4 and 0.63 kcal mol−1 of 5, which confirms the experimentally observed impossibility of the tautomeric equilibrium in the former. The experimentally observed specific solvent effect in methanol is modeled via explicit solvation. The excited state intramolecular proton transfer (ESIPT) was investigated by steady state fluorescence spectroscopy. Both compounds show a high rate of photoconversion to keto tautomers hence keto emissions with large Stokes shifts in five alcohols (MeOH, EtOH, 1-propanol, 1-butanol, and 1-pentanol) and various aprotic solvents (toluene, dichlormethane, acetone, AcCN). According to the excited state TDDFT calculations using implicit solvation in MeOH, it was found that enol tautomers of 4 and 5 are higher in energy compared to the keto ones, which explains the origin of the experimentally observed keto form emission.Item INHIBITING SEDIMENT FORMATION IN AN EXTRA LIGHT CRUDE OIL AND IN A HYDROCRACKED ATMOSPHERIC RESIDUE BY COMMERCIAL CHEMICAL ADDITIVES(2022-01-01) Stratiev D.; Shishkova I.; Tavlieva M.; Kirilov K.; Dinkov R.; Yordanov D.; Yankova L.; Toteva V.; Nikolova R.Extra light crude oil from Kazahstan and hydrocracked atmospheric residue from a commercial ebullated bed vacuum residue hydrocracker were investigated to reduce their sediment formation rate by employing 13 commercial chemical additives. Ten of the studied additives were based on the organic acid derivatives. Asphaltene dispersion test was applied in this study to define the most appropriate chemical additive and the optimum treating rate. The additives demonstrated different performance with the distinct oils. All organic acid derivative additives were capable of suppressing the sedimentation in the hydrocracked atmospheric residue, while not all of them were effective in decreasing the sediment formation in the extra light petroleum. The phosphoric acid and poly-iso-butylene succinimide based additives were effective in suppressing the sedimentation in the hydrocracked atmospheric residue while they promoted the formation of sediments in the extra light petroleum. The additive based on 1,2,4-trimethylbenzene was ineffective in decreasing the sedimentation in the hydrocracked atmospheric residue and slightly effective in the suppression of sediment formation in the extra light petroleum.Item Intercriteria Analysis to Diagnose the Reasons for Increased Fouling in a Commercial Ebullated Bed Vacuum Residue Hydrocracker(2022-01-01) Stratiev D.; Shishkova I.; Dinkov R.; Kolev I.; Argirov G.; Ivanov V.; Ribagin S.; Atanassova V.; Atanassov K.; Stratiev D.; Nenov S.; Pilev D.; Yordanov D.The intercriteria analysis developed on the base of intuitionistic fuzziness and index matrices was applied to evaluate processing data of the LUKOIL Neftohim Burgas H-Oil ebullated bed vacuum residue hydrocracker with the aim of revealing the reasons for increased fouling registered during the 3rd cycle of the H-Oil hydrocracker. It was found that when the ratio of the δT of the 1st reactor to the δT of the 2nd reactor gets lower than 2.0, an excessive H-Oil equipment fouling occurs. The fouling was also found to be favored by processing of lower Conradson carbon content vacuum residual oils and increased throughput and depressed by increasing the dosage of the HCAT nanodispersed catalyst. The fouling in the atmospheric tower bottom section is facilitated by a lower aromatic content in the atmospheric tower bottom product. The addition of FCC slurry oil not only increases aromatic content but also dissolves some of the asphaltenes in the atmospheric residual hydrocracked oil and decreases its colloidal instability index. The fouling in the vacuum tower bottom section is facilitated by a higher saturate content in the VTB. Surprisingly, it was found that the asphaltene content in the VTB depresses the fouling rate. No relation was found of the sediment content in the hydrocracked residual oils measured by hot filtration tests and by the centrifuge method to the equipment fouling of the H-Oil hydrocracker.Item Petroleum Crude Slate, Catalyst Properties and H-Oil VGO Properties Effects on a Commercial FCC Unit Performance(2021-01-01) Stratiev D.; Shishkova I.; Petrov I.; Yordanov D.; Toteva V.The performance of the commercial LUKOIL Neftohim Burgas fluid catalytic cracking unit (LNB FCCU) during processing 24 blends of straight run vacuum gas oils originating from 16 petroleum crudes and an imported atmospheric residue and employment of four catalysts was evaluated. It was found that the nature of the petroleum crudes processed in the ratios employed had no effect on the LNB FCCU performance. Instead, the content of the H-Oil vacuum gas oil (VGO) and its quality quantified by Kw-characterization factor was found to control the LNB FCCU conversion level. Based on the LNB FCCU commercial data a regression was developed quantifying the effect of equilibrium catalyst activity, H-Oil quality, and quantity in the fluid catalytic cracking (FCC) feed, and catalyst-to-oil ratio on the level of conversion. The regression was used to evaluate the impact of catalyst activity and catalyst-to-oil ratio, that is known to be a function of catalyst Δ coke selectivity, on the FCC conversion.Item Predicting Petroleum SARA Composition from Density, Sulfur Content, Flash Point, and Simulated Distillation Data Using Regression and Artificial Neural Network Techniques(2024-08-01) Shiskova I.; Stratiev D.; Sotirov S.; Sotirova E.; Dinkov R.; Kolev I.; Stratiev D.D.; Nenov S.; Ribagin S.; Atanassov K.; Yordanov D.; van den Berg F.The saturate, aromatic, resin, and asphaltene content in petroleum (SARA composition) provides valuable information about the chemical nature of oils, oil compatibility, colloidal stability, fouling potential, and other important aspects in petroleum chemistry and processing. For that reason, SARA composition data are important for petroleum engineering research and practice. Unfortunately, the results of SARA composition measurements reported by diverse laboratories are frequently very dissimilar and the development of a method to assign SARA composition from oil bulk properties is a question that deserves attention. Petroleum fluids with great variability of SARA composition were employed in this study to model their SARA fraction contents from their density, flash point, sulfur content, and simulated distillation characteristics. Three data mining techniques: intercriteria analysis, regression, and artificial neural networks (ANNs) were applied. It was found that the ANN models predicted with higher accuracy the contents of resins and asphaltenes, whereas the non-linear regression model predicted most accurately the saturate fraction content but with an accuracy that was lower than that reported in the literature regarding uncertainty of measurement. The aromatic content was poorly predicted by all investigated techniques, although the prediction of aromatic content was within the uncertainty of measurement. The performed study suggests that as well as the investigated properties, additional characteristics need to be explored to account for complex petroleum chemistry in order to improve the accuracy of SARA composition prognosis.Item Prediction of Molecular Weight of Petroleum Fluids by Empirical Correlations and Artificial Neuron Networks(2023-02-01) Stratiev D.; Sotirov S.; Sotirova E.; Nenov S.; Dinkov R.; Shishkova I.; Kolev I.V.; Yordanov D.; Vasilev S.; Atanassov K.; Simeonov S.; Palichev G.N.The exactitude of petroleum fluid molecular weight correlations affects significantly the precision of petroleum engineering calculations and can make process design and trouble-shooting inaccurate. Some of the methods in the literature to predict petroleum fluid molecular weight are used in commercial software process simulators. According to statements made in the literature, the correlations of Lee–Kesler and Twu are the most used in petroleum engineering, and the other methods do not exhibit any significant advantages over the Lee–Kesler and Twu correlations. In order to verify which of the proposed in the literature correlations are the most appropriate for petroleum fluids with molecular weight variation between 70 and 1685 g/mol, 430 data points for boiling point, specific gravity, and molecular weight of petroleum fluids and individual hydrocarbons were extracted from 17 literature sources. Besides the existing correlations in the literature, two different techniques, nonlinear regression and artificial neural network (ANN), were employed to model the molecular weight of the 430 petroleum fluid samples. It was found that the ANN model demonstrated the best accuracy of prediction with a relative standard error (RSE) of 7.2%, followed by the newly developed nonlinear regression correlation with an RSE of 10.9%. The best available molecular weight correlations in the literature were those of API (RSE = 12.4%), Goosens (RSE = 13.9%); and Riazi and Daubert (RSE = 15.2%). The well known molecular weight correlations of Lee–Kesler, and Twu, for the data set of 430 data points, exhibited RSEs of 26.5, and 30.3% respectively.Item Prediction of Refractive Index of Petroleum Fluids by Empirical Correlations and ANN(2023-08-01) Palichev G.N.; Stratiev D.; Sotirov S.; Sotirova E.; Nenov S.; Shishkova I.; Dinkov R.; Atanassov K.; Ribagin S.; Stratiev D.D.; Pilev D.; Yordanov D.The refractive index is an important physical property that is used to estimate the structural characteristics, thermodynamic, and transport properties of petroleum fluids, and to determine the onset of asphaltene flocculation. Unfortunately, the refractive index of opaque petroleum fluids cannot be measured unless special experimental techniques or dilution is used. For that reason, empirical correlations, and metaheuristic models were developed to predict the refractive index of petroleum fluids based on density, boiling point, and SARA fraction composition. The capability of these methods to accurately predict refractive index is discussed in this research with the aim of contrasting the empirical correlations with the artificial neural network modelling approach. Three data sets consisting of specific gravity and boiling point of 254 petroleum fractions, individual hydrocarbons, and hetero-compounds (Set 1); specific gravity and molecular weight of 136 crude oils (Set 2); and specific gravity, molecular weight, and SARA composition data of 102 crude oils (Set 3) were used to test eight empirical correlations available in the literature to predict the refractive index. Additionally, three new empirical correlations and three artificial neural network (ANN) models were developed for the three data sets using computer algebra system Maple, NLPSolve with Modified Newton Iterative Method, and Matlab. For Set 1, the most accurate refractive index prediction was achieved by the ANN model, with %AAD of 0.26% followed by the new developed correlation for Set 1 with %AAD of 0.37%. The best literature empirical correlation found for Set 1 was that of Riazi and Daubert (1987), which had %AAD of 0.40%. For Set 2, the best performers were the models of ANN, and the new developed correlation of Set 2 with %AAD of refractive index prediction was 0.21%, and 0.22%, respectively. For Set 3, the ANN model exhibited %AAD of refractive index prediction of 0.156% followed by the newly developed correlation for Set 3 with %AAD of 0.163%, while the empirical correlations of Fan et al. (2002) and Chamkalani (2012) displayed %AAD of 0.584 and 0.552%, respectively.Item Role of Catalyst in Optimizing Fluid Catalytic Cracking Performance during Cracking of H-Oil-Derived Gas Oils(2021-03-23) Stratiev D.; Shishkova I.; Ivanov M.; Dinkov R.; Georgiev B.; Argirov G.; Atanassova V.; Vassilev P.; Atanassov K.; Yordanov D.; Popov A.; Padovani A.; Hartmann U.; Brandt S.; Nenov S.; Sotirov S.; Sotirova E.Three H-Oil gas oils, heavy atmospheric gas oil (HAGO), light vacuum gas oil (LVGO), heavy vacuum gas oil (HVGO), and two their blends with hydrotreated straight run vacuum gas oils (HTSRVGOs) were cracked on two high unit cell size (UCS) lower porosity commercial catalysts and two low UCS higher porosity commercial catalysts. The cracking experiments were performed in an advanced cracking evaluation fluid catalytic cracking (FCC) laboratory unit at 527 °C, 30 s catalyst time on stream, and catalyst-to-oil (CTO) variation between 3.5 and 7.5 wt/wt The two high UCS lower porosity catalysts were more active and more coke selective. However, the difference between conversion of the more active high UCS lower porosity and low UCS higher porosity catalysts at 7.5 wt/wt CTO decreased in the order 10% (HAGO) > 9% (LVGO) > 6% (HVGO) > 4% (80% HTSRVGO/20% H-Oil VGO). Therefore, the catalyst performance is feedstock-dependent. The four studied catalysts along with a blend of one of them with 2% ZSM-5 were examined in a commercially revamped UOP FCC VSS unit. The lower UCS higher porosity catalysts exhibited operation at a higher CTO ratio achieving a similar conversion level with more active higher UCS lower porosity catalysts. However, the higher UCS lower porosity catalysts made 0.67% Δcoke that was higher than the maximum acceptable limit of 0.64% for this particular commercial FCC unit (FCCU), which required excluding the HVGO from the FCC feed blend. The catalyst system containing ZSM-5 increased the LPG yield but did not have an impact on gasoline octane. It was found that the predominant factor that controls refinery profitability related to the FCCU performance is the FCC slurry oil (bottoms) yield.Item SAR-AD Method to Characterize Eight SARA Fractions in Various Vacuum Residues and Follow Their Transformations Occurring during Hydrocracking and Pyrolysis(2023-04-01) Adams J.J.; Rovani J.F.; Planche J.P.; Loveridge J.; Literati A.; Shishkova I.; Palichev G.; Kolev I.; Atanassov K.; Nenov S.; Ribagin S.; Stratiev D.; Yordanov D.; Huo J.Model compounds were used to provide some chemical boundaries for the eight-fraction SAR-ADTM characterization method for heavy oils. It was found that the Saturates fraction consists of linear and highly cyclic alkanes; the Aro-1 fraction consists of molecules with a single aromatic ring; the Aro-2 fraction consists of mostly 2 and 3-ring fused aromatic molecules, the pericondensed 4-ring molecule pyrene, and molecules with 3–5 rings that are not fused; and the Aro-3 fraction consists of 4-membered linear and catacondensed aromatics, larger pericondensed aromatics, and large polycyclic aromatic hydrocarbons. The Resins fraction consists of mostly fused aromatic ring systems containing polar functional groups and metallated polar vanadium oxide porphyrin compounds, and the Asphaltene fraction consists of both island- and archipelago-type structures with a broad range of molecular weight variation, aromaticity, and heteroatom contents. The behavior of the eight SAR-ADTM fractions during hydrocracking and pyrolysis was investigated, and quantitative relations were established. Intercriteria analysis and evaluation of SAR-ADTM data of hydrocracked vacuum residue and sediment formation rate in commercial ebullated bed vacuum residue hydrocracking were performed. It showed that total asphaltene content, toluene-soluble asphaltenes, and colloidal instability index contribute to sediment formation, while Resins and Cyclohexane-soluble asphaltenes had no statistically meaningful relation to sediment formation for the studied range of operation conditions.Item Tautomeric influence on the photoinduced birefringence of 4-substituted phthalimide 2-hydroxy Schiff bases in PMMA matrix(2021-05-01) Blagoeva B.; Stoilova A.; Dimov D.; Yordanov D.; Nazarova D.; Georgiev A.; Antonov L.The photoinduced birefringence of two 4-substituted phthalimide 2-hydroxy Schiff bases, containing salicylic (4) and 2-hydroxy-1-naphthyl (5) moieties has been investigated in PMMA matrix. Their optical behaviour as nanocomposite films was revealed by combined use of DFT quantum chemical calculations (in ground and excited state) and experimental optical spectroscopy (UV–Vis and fluorescence). The results have shown that solid-state reversible switching takes place by enol/keto tautomerization and Z/E isomerization. Birefringence study was performed in the PMMA nanocomposite films using pump lasers at λrec = 355 nm and λrec = 442 nm. Fast response time and high stability of anisotropy up to 58% for (4) and 95% for (5) after turning off the excitation laser, was observed, which makes these materials appropriate candidates for cutting-edge optical information technology materials. The possibility for multiple cycles of recording, reading and optical erasure of the photoinduced birefringence at λrec = 442 nm in 5 has been demonstrated. The obtained results have shown that the maximum value of the measured birefringence is close to the anisotropic characteristics of the most frequently used azo materials.