Browsing by Author "Ribagin S."
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Item Challenges in Petroleum Characterization—A Review(2022-10-01) Shishkova I.; Stratiev D.; Kolev I.V.; Nenov S.; Nedanovski D.; Atanassov K.; Ivanov V.; Ribagin S.252 literature sources and about 5000 crude oil assays were reviewed in this work. The review has shown that the petroleum characterization can be classified in three categories: crude oil assay; SARA characterization; and molecular characterization. It was found that the range of petroleum property variation is so wide that the same crude oil property cannot be measured by the use of a single standard method. To the best of our knowledge for the first time the application of the additive rule to predict crude oil asphaltene content from that of the vacuum residue multiplied by the vacuum residue TBP yield was examined. It was also discovered that a strong linear relation between the contents of C5-, and C7-asphaltenes in crude oil and derived thereof vacuum residue fraction exists. The six parameter Weibull extreme function showed to best fit the TBP data of all crude oil types, allowing construction of a correct TBP curve and detection of measurement errors. A new SARA reconstitution approach is proposed to overcome the poor SARA analysis mass balance when crude oils with lower density are analyzed. The use of a chemometric approach with combination of spectroscopic data was found very helpful in extracting information about the composition of complex petroleum matrices consisting of a large number of components.Item COMMERCIAL AND LABORATORY EXPERIENCE WITH CATALYTIC CRACKING OF STRAIGHT RUN HYDROTREATED VACUUM GAS OIL AND H-OIL GAS OILS(2022-01-01) Stratiev D.; Shishkova I.; Ivanov M.; Petrov I.; Atanassova V.; Ribagin S.; Atanassov K.; Toteva V.; Stratiev D.This study presents for the first time an investigation of fluid catalytic cracking of 100 % H-vacuum gas oil at a commercial FCC unit. 100 % straight run hydrotreated vacuum gas oil (HTSRVGO) and 100 % H-vacuum gas oil have been cracked in the commercial LUKOIL Neftohim Burgas fluid catalytic cracking and in a laboratory confined ebbulated bed ACE catalytic cracking unit. The relations between the operating conditions of the commercial FCC unit and conversion level in both cases 100 % HTSRVGO and its blends with H-Oil VGO were investigated using intercriteria analysis. Multiple regressions were developed to quantify the effect of the operating conditions as well as quantity and quality of H-Oil VGO on conversion level in the commercial FCC unit. ACE laboratory tests with feed containing about 20 % H-Oil VGO at different catalyst-to-oil ratios and reaction temperature were performed and the results are discussed.Item Commercial Ebullated Bed Vacuum Residue Hydrocracking Performance Improvement during Processing Difficult Feeds(2023-03-01) Georgiev B.E.; Stratiev D.S.; Argirov G.S.; Nedelchev A.; Dinkov R.; Shishkova I.K.; Ivanov M.; Atanassov K.; Ribagin S.; Nikolov Palichev G.; Nenov S.; Sotirov S.; Sotirova E.; Pilev D.; Stratiev D.D.The Urals and Siberian vacuum residues are considered difficult to process in the ebullated bed hydrocracking because of their increased tendency to form sediments. Their achievable conversion rate reported in the literature is 60%. Intercriteria analysis was used to assess data from a commercial vacuum residue hydrocracker during processing blends from three vacuum residues: Urals, Siberian Light, and Basra Heavy. The analysis revealed that the main contributors to conversion enhancement is hydrodemetallization (HDM) and the first reactor ΔT augmentation. The increase of HDM from 40 to 98% and the first reactor ΔT (ΔT(R1)) from 49 to 91 °C were associated with a vacuum residue conversion enhancement of 62.0 to 82.7 wt.%. The developed nonlinear regression prediction of conversion from HDM and ΔT(R1) suggests a bigger influence of ΔT(R1) enhancement on conversion augmentation than the HDM increase. The intercriteria analysis evaluation revealed that the higher first reactor ΔT suppresses the sediment formation rate to a greater extent than the higher HDM. During processing Basrah Heavy vacuum residue, a reduction in hydrodeasphaltization (HDAs) from 73.6 to 55.2% and HDM from 88 to 81% was observed. It was confirmed that HDM and HDAs are interrelated. It was found that the attainment of conversion of 80 wt.% and higher during processing Urals and Siberian Light vacuum residues is possible when the HDM is about 90% and LHSV ≤ 0.19 h−1.Item Correlations of HTSD to TBP and Bulk Properties to Saturate Content of a Wide Variety of Crude Oils(2023-02-01) Stratiev D.; Dinkov R.; Tavlieva M.; Shishkova I.; Nikolov Palichev G.; Ribagin S.; Atanassov K.; Stratiev D.D.; Nenov S.; Pilev D.; Sotirov S.; Sotirova E.; Simeonov S.; Boyadzhieva V.Forty-eight crude oils with variations in specific gravity (0.782 ≤ SG ≤ 1.002), sulphur content (0.03 ≤ S ≤ 5.6 wt.%), saturate content (23.5 ≤ Sat. ≤ 92.9 wt.%), asphaltene content (0.1 ≤ As ≤ 22.2 wt.%), and vacuum residue content (1.4 ≤ VR ≤ 60.7 wt.%) were characterized with HTSD, TBP, and SARA analyses. A modified SARA analysis of petroleum that allows for the attainment of a mass balance ≥97 wt.% for light crude oils was proposed, a procedure for the simulation of petroleum TBP curves from HTSD data using nonlinear regression and Riazi’s distribution model was developed, and a new correlation to predict petroleum saturate content from specific gravity and pour point with an average absolute deviation of 2.5 wt.%, maximum absolute deviation of 6.6 wt.%, and bias of 0.01 wt.% was developed. Intercriteria analysis was employed to evaluate the presence of statistically meaningful relations between the different petroleum properties and to evaluate the extent of similarity between the studied petroleum crudes. It was found that the extent of similarity between the crude oils based on HTSD analysis data could be discerned from data on the Kw characterization factor of narrow crude oil fractions. The results from this study showed that contrary to the generally accepted concept of the constant Kw characterization factor, the Kw factors of narrow fractions differ from that of crude oil. Moreover, the distributions of Kw factors of the different crudes were different.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 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 Experience in Processing Alternative Crude Oils to Replace Design Oil in the Refinery(2024-06-01) Stratiev D.; Shiskova I.; Toteva V.; Georgiev G.; Dinkov R.; Kolev I.; Petrov I.; Argirov G.; Bureva V.; Ribagin S.; Atanassov K.; Nenov S.; Sotirov S.; Nikolova R.; Veli A.A comprehensive investigation of a highly complex petroleum refinery (Nelson complexity index of 10.7) during the processing of 11 crude oils and an imported atmospheric residue replacing the design Urals crude oil was performed. Various laboratory oil tests were carried out to characterize both crude oils, and their fractions. The results of oil laboratory assays along with intercriteria and regression analyses were employed to find quantitative relations between crude oil mixture quality and refining unit performance. It was found that the acidity of petroleum cannot be judged by its total acid number, and acid crudes with lower than 0.5 mg KOH/g and low sulphur content required repeated caustic treatment enhancement and provoked increased corrosion rate and sodium contamination of the hydrocracking catalyst. Increased fouling in the H-Oil hydrocracker was observed during the transfer of design Urals crude oil to other petroleum crudes. The vacuum residues with higher sulphur, lower nitrogen contents, and a lower colloidal instability index provide a higher conversion rate and lower fouling rate in the H-Oil unit. The regression equations developed in this work allow quantitative assessment of the performance of crucial refining units like the H-Oil, fluid catalytic cracker, naphtha reformer, and gas oil hydrotreatment based on laboratory oil test results.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 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 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 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 Study of Bulk Properties Relation to SARA Composition Data of Various Vacuum Residues Employing Intercriteria Analysis(2022-12-01) Stratiev D.; Shishkova I.; Palichev G.N.; Atanassov K.; Ribagin S.; Nenov S.; Nedanovski D.; Ivanov V.Twenty-two straight run vacuum residues extracted from extra light, light, medium, heavy, and extra heavy crude oils and nine different hydrocracked vacuum residues were characterized for their bulk properties and SARA composition using four and eight fractions (SAR-ADTM) methods. Intercriteria analysis was employed to determine the statistically meaningful relations between the SARA composition data and the bulk properties. The determined strong relations were modeled using the computer algebra system Maple and NLPSolve with the Modified Newton Iterative Method. It was found that the SAR-ADTM saturates, and the sum of the contents of saturates and ARO-1 can be predicted from vacuum residue density, while the SAR-ADTM asphaltene fraction content, and the sum of asphaltenes, and resins contents correlate with the softening point of the straight run vacuum residues. The softening point of hydrocracked vacuum residues was found to strongly negatively correlates with SAR-ADTM Aro-1 fraction, and strongly positively correlates with SAR-ADTM Aro-3 fraction. While in the straight run vacuum residues, the softening point is controlled by the content of SAR-ADTM asphaltene fraction in the H-Oil hydrocracked vacuum residues, the softening point is controlled by the content of SAR-ADTM Aro-3 fraction content. During high severity H-Oil operation, resulting in higher conversion, hydrocracked vacuum residue with higher SAR-ADTM Aro-3 fraction content is obtained, which makes it harder and more brittle.