Hydrocracking Of Vacuum Residue Research Articles

Structural design and electronic regulation of atomically dispersed Mo-S4 sites by second shell N species reconfiguration for intensifying hydrogen spillover

Intensifying hydrogen spillover by regulating the atomic local structures catalysts is crucial for improving the hydrogenation performance, but still hugely challenging. Herein, we report a robust single-atom catalyst featuring Mo-S4 sites in the first shell modulated with N atoms in the second shell (Mo-S4-N/C) by an efficient cyclodextrin supramolecular self-assembly pyrolysis strategy for intensifying hydrogen spillover in slurry-phase hydrocracking of vacuum residue (VR). We discovered that the H2 is activated at the single-atom Mo-S4 sites efficiently and the spillover of active hydrogen is accelerated by the reconfiguration of N species in the second shell. Remarkably, the Mo-S4-N/C catalyst demonstrates excellent catalytic hydrogenation activity with high turnover frequency calculated for total metals up to 0.46 s−1, the VR per pass conversion of 61 wt.%, liquid product yield of 94 wt.%, and the low coke content of 0.6 wt.%, along with good stability, respectively. Theoretical calculations revealed that the N species in the second shell regulated the electronic structure of Mo-S4 sites, promoting the migration of active hydrogen species by reducing the transfer energy barrier of hydrogen spillover, thus enhancing the hydrogenation performance. This work proposed a strengthened hydrogen spillover mechanism from the atomic scale for hydrogenation reaction, offering novel concepts for designing and developing high-performance hydrogenation catalysts.

Roles of Catalysts and Feedstock in Optimizing the Performance of Heavy Fraction Conversion Processes: Fluid Catalytic Cracking and Ebullated Bed Vacuum Residue Hydrocracking

Petroleum refining has been, is still, and is expected to remain in the next decades the main source of energy required to drive transport for mankind. The demand for automotive and aviation fuels has urged refiners to search for ways to extract more light oil products per barrel of crude oil. The heavy oil conversion processes of ebullated bed vacuum residue hydrocracking (EBVRHC) and fluid catalytic cracking (FCC) can assist refiners in their aim to produce more transportation fuels and feeds for petrochemistry from a ton of petroleum. However, a good understanding of the roles of feed quality and catalyst characteristics is needed to optimize the performance of both heavy oil conversion processes. Three knowledge discovery database techniques—intercriteria and regression analyses, and artificial neural networks—were used to evaluate the performance of commercial FCC and EBVRHC in processing 19 different heavy oils. Seven diverse FCC catalysts were assessed using a cascade and parallel fresh catalyst addition system in an EBVRHC unit. It was found that the vacuum residue conversion in the EBVRHC depended on feed reactivity, which, calculated on the basis of pilot plant tests, varied by 16.4%; the content of vacuum residue (VR) in the mixed EBVRHC unit feed (each 10% fluctuation in VR content leads to an alteration in VR conversion of 1.6%); the reaction temperature (a 1 °C deviation in reaction temperature is associated with a 0.8% shift in VR conversion); and the liquid hourly space velocity (0.01 h-1 change of LHSV leads to 0.85% conversion alteration). The vacuum gas oil conversion in the FCC unit was determined to correlate with feed crackability, which, calculated on the basis of pilot plant tests, varied by 8.2%, and the catalyst ΔCoke (each 0.03% ΔCoke increase reduces FCC conversion by 1%), which was unveiled to depend on FCC feed density and equilibrium FCC micro-activity. The developed correlations can be used to optimize the performance of FCC and EBVRHC units by selecting the appropriate feed slate and catalyst.

Preparation of presulfided oil-soluble NiMo catalyst for slurry bed hydrocracking of vacuum residue

Here, a method is proposed for constructing presulfided oil-soluble NiMo catalysts using tetrathiomolybdate nickel ammonium as a precursor via a chelating ligand exchange strategy. Leveraging the close chemical bonding between Ni and Mo atoms, the NiMo catalyst can undergo in-situ self-sulfidation to generate active NiMoS sites and a composite structure of Ni3S2 and MoS2 nano phase in tight contact, thus exhibiting strong synergistic effects. The NiMo catalyst exhibited outstanding performance in hydrocracking of vacuum residue (VR) achieving a 64.7 wt% VR conversion while maintaining a coke yield of 0.51 wt%, as well as the excellent hydrogenation activity of polycyclic aromatic hydrocarbons. Combined with density functional theory calculations, it was further revealed that the presence of Ni reduces the energy barrier for H2 dissociation on MoS2, thereby enhancing the hydrogenation activity of the catalyst and its ability to suppress coke formation. This work validates the efficient bimetallic synergistic catalytic effect of presulfided oil-soluble NiMo catalysts in the slurry bed hydrocracking process.

Industrial Investigation of the Combined Action of Vacuum Residue Hydrocracking and Vacuum Gas Oil Catalytic Cracking While Processing Different Feeds and Operating under Distinct Conditions

Ebullated bed vacuum residue hydrocracking and fluid catalytic cracking (FCC) are among the most profitable processes in modern refining. Their optimal performance is vital for petroleum refining profitability. That is why a better understanding of their combined action and the interrelations between these two heavy oil conversion processes in a real-world refinery could provide valuable information for further performance optimization. Nine distinct petroleum crudes belonging to the extra light, light, and medium petroleum crude types were processed in the LUKOIL Neftohim Burgas refinery to study the combined performance of two processes: FCC of vacuum gas oil and ebullated bed vacuum residue H-Oil hydrocracking. The operating conditions along with the characterization data of the feeds and products of both processes were evaluated through the employment of intercriteria analysis to define the variables with statistically significant relationships. Maple 2023 Academic Edition mathematics software was used to develop models to predict the vacuum residue conversion level under different operating conditions. The plug flow reactor model with an activation energy of 215 kJ/mol and a reaction order of 1.59 was found to provide the highest accuracy of vacuum residue conversion, with an average absolute deviation of 2.2%. H-Oil yields were found to correlate with the vacuum residue conversion level and the content of FCC slurry oil (SLO), the recycling of partially blended fuel oil, a material boiling point below 360 °C, and the vacuum gas oil (VGO) in the H-Oil feed. FCC conversion was found to depend on the H-Oil VGO content in the FCC feed and the content of FCC SLO in the H-Oil feed.

Comparative study of single- and two-stage slurry-phase catalytic hydrocracking of vacuum residue for selective conversion of heavy oil

The selective conversion of asphaltenes to light products while inhibiting coke formation is the most challenging in the heavy oil upgrading process. Herein, single- and two-stage slurry-phase catalytic hydrocracking of vacuum residue (VR) at various reaction temperatures (350–430 °C) were performed to elucidate the advantages of low temperature conditions and the synergistic effect of two-stage operation on asphaltene conversion. Despite the slow reaction rate at a low reaction temperature, almost no coke was produced, and the selective conversion of asphaltene to deasphalted oil (DAO) was improved with a large amount of H2 consumption. To overcome the low reaction rates at low temperatures, catalytic hydrocracking was performed at two-stage temperatures (380 and 430 °C). Two-stage catalytic hydrocracking showed a synergistic effect of suppressing coke formation while maintaining an enhanced reaction rate compared to single-stage catalytic hydrocracking. This is because the first stage of hydrocracking at 380 °C facilitates the saturation of heavy polyaromatic molecules, which can easily crack in the second stage at 430 °C. However, because two-stage hydrocracking requires a slightly longer reaction time than single-stage hydrocracking to achieve the same conversion, the efficiency of asphaltene conversion must be considered by setting appropriate operating conditions.

The effect of recycle stream on slurry-phase hydrocracking of vacuum residue: An experimental and modeling approach

The effect of the recycle stream on slurry-phase hydrocracking (HCK) of vacuum residue was examined using a continuous bench-scale unit with the aim of attaining process optimization. This was achieved through a model-based approach that links experimental investigations, kinetic modeling, and model-based optimization. The experiments were conducted at various reaction temperatures, liquid hourly space velocity of fresh feed (LHSVFF) and recycle ratios at a pressure of 160 bar, with the fresh feed containing 1000 wt. ppm of molybdenum. The HCK kinetic model was modified to incorporate the recycling effects and accurately predict the experimental data. The adapted model confirmed that the unconverted residue in recycle operating mode (ROM) became more refractory. By implementing the modified kinetic model in a dynamic Simulink model, the prediction accuracy of RES conversions and product yields can be improved by up to 25.1 wt.% in the case of the lowest conversion. A sensitivity analysis using the dynamic model showed that the temperature exerted a greater impact on the RES conversion and recycle ratio in ROM. An operational stability index was also proposed to prevent operation failure in ROM. Finally, an optimal operating condition from the parametric study was found to meet several process goals simultaneously.

The Effect of Carbon Nanofibers on the Hydrocracking of Vacuum Residue in the Presence of Formic Acid

This study was devoted to the processing of vacuum residue to produce lighter oil fractions, such as gasoline and diesel fuel. The hydrocracking and catalytic hydrocracking of vacuum residue in the presence of formic acid (FA) were performed in the temperature range of 250–550 °C. Carbon nanofibers (CNFs) were used as catalytic additives. In contrast to conventional hydrocracking, an important stage in the catalytic hydrocracking of vacuum residue is the decomposition of formic acid. Experimental studies on the effect of CNFs on the decomposition of FA demonstrated that CNFs pre-treated in a NaOH solution (CNF (NaOH)s) had the highest activity and selectivity for the production of H2 and CO2. The maximum yield of liquid products in the catalytic hydrocracking process, equal to 34 wt.%, was observed at 300 °C in the presence of CNF (NaOH)s. The characterization of the fractional compositions of the liquid products showed that the ratios of the fractions changed with an increase in the reaction temperature. The maximum concentrations of the light fractions (gasoline and diesel) in the liquid products of the catalytic hydrocracking of vacuum residue were observed at 300–350 °C in the presence of CNF (NaOH)s.

Modelling of a vacuum residue hydrocracking in an industrial slurry phase reactor

AbstractThe upgradation of the bottom of the barrel has gained much interest across the refineries due to severe environmental rules, limitations of conventional oil reserves, and its flexibility to produce light end products which benefit end users. Slurry phase hydrocracking is one of the growing technologies to fulfil the increasing demand for light cut. Modelling of an industrial slurry phase reactor (SPR) for vacuum residue hydrocracking using different kinetic models is proposed. The axial dispersion model (ADM) is used for modelling an industrial SPR. The mathematical model of the reactors is incorporated for the three different lump kinetic models. This study deals with the continuous stirred tank reactor (CSTR) and SPR modelling, followed by industrial SPR modelling. The small lab‐scale reactor models are validated with the experimental data reported in the literature. The study's objective was to investigate the one‐dimensional and two‐dimensional concentration dynamics of each lump along the axial and radial positions of industrial SPR. The vacuum residue conversion into the light fractions was obtained by more than 73% in industrial SPR. Also, the yield of vacuum gas oil and resins were evaluated as 49% and 63%, respectively. The sensitivity analysis was performed to explain the effect of process variables. The optimum range was found as a length of 15 m, liquid hourly space velocity (LHSV) of 0.2 h−1, 1% catalyst concentration, and 420°C reaction temperature to enhance the throughput of the reactor.

SAR-AD Method to Characterize Eight SARA Fractions in Various Vacuum Residues and Follow Their Transformations Occurring during Hydrocracking and Pyrolysis

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.

Commercial Ebullated Bed Vacuum Residue Hydrocracking Performance Improvement during Processing Difficult Feeds

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.

Highly active and stable CoWS2 catalysts in slurry phase hydrocracking of vacuum residue: XAFS studies

The bimetallic CoWS2 catalysts were prepared in situ during the slurry phase hydrocracking (HCK) of vacuum residue (VR) using W(CO)6 and Co-octoate as oil soluble precursors to investigate the promotional effect of Co promoters on the dispersed WS2 catalyst for the VR HCK. The morphologies and structural properties of dispersed catalysts were characterized by transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS). The bimetallic CoWS2 catalyst was observed to form well-dispersed monolayers in the size range of 7–11 nm, which showed higher turn-over frequency values (TOF) and C7-asphaltene (C7-ASP) conversions than monometallic WS2 or Co9S8 catalysts in the VR HCK at 693 K and 10.0 MPa H2. Moreover, the extended X-ray fine absorption structure spectroscopy (EXAFS) coupled with the density functional theory (DFT) calculations successfully verified the formation of the Co-W-S phase.

Application of Ebullated-Bed Vacuum Residue Hydrocracking at Lukoil Neftohim Burgas

Application of Ebullated-Bed Vacuum Residue Hydrocracking at Lukoil Neftohim Burgas

Impacts of support properties on the vacuum residue slurry-phase hydrocracking performance of Mo catalysts

To deeply understand the effects of support properties on the performance of Mo-based slurry-phase hydrocracking catalysts, four Mo-based catalysts supported on amorphous silica alumina (ASA), γ-Al2O3, ultra-stable Y (USY) zeolite and SiO2 were prepared by the incipient wetness impregnation method, respectively, and their catalytic performances were compared in the vacuum residue (VR) hydrocracking process. It is found that the Mo/ASA catalyst exhibits the highest VR conversion among the different catalysts, indicating that both the appropriate amount of acid sites, especially B acid sites and larger mesoporous volume of ASA can enhance the VR hydrocracking into light distillates. Furthermore, Mo catalysts supported on the different supports show quite different product distributions in VR hydrocracking. The Mo/ASA catalyst provides higher yields of naphtha and middle distillates and lower yields of gas and coke compared with other catalysts, it is attributed to the highest MoS2 slab dispersion, the highest sulfuration degree of Mo species, and the most Mo atoms located at the edge sites for the Mo/ASA catalyst, as observed by HRTEM and XPS analyses. These features of Mo/ASA are beneficial for the hydrogenation of intermediate products and polycyclic aromatic hydrocarbons to restrict the gas and coke formation.

Atomic coordination structural dynamic evolution of single-atom Mo catalyst for promoting H2 activation in slurry phase hydrocracking

Development of efficient catalysts with high atomic utilization and turnover frequency (TOF) for H2 activation in slurry phase hydrocracking (SPHC) is crucial for the conversion of vacuum residue (VR). Herein, for the first time, we reported a robust and stable single atoms (SAs) Mo catalyst through a polymerization-pyrolysis-in situ sulfurization strategy for activating H2 in SPHC of VR. An interesting atomic coordination structural dynamic evolution of Mo active sites was discovered. During hydrocracking of VR, the O atoms that coordinated with Mo were gradually replaced by S atoms, which led to the O/S exchange process. The coordination structure of the Mo SAs changed from pre-reaction Mo-O3S1 to post-reaction Mo-O1S3 coordination configurations, promoting the efficient homolytic cleavage activation of H2 into H radical species effectively. The evolved Mo SAs catalyst exhibited robust catalytic hydrogenation activity with the per pass conversion of VR of 65 wt%, product yield of liquid oils of 93 wt%, coke content of only 0.63 wt%, TOF calculated for total metals up to 0.35 s−1, and good cyclic stability. Theoretical calculation reveals that the significant variation of occupied Mo 4d states before and after H2 interaction has a direct bearing on the dynamic evolution of Mo SAs catalyst structure. The lower d-band center of Mo-O1S3 site indicates that atomic H diffusion is easy, which is conducive to catalytic hydrogenation. The finding of this study is of great significance to the development of high atom economy catalysts for the industrial application of heavy oil upgrading technology.

Опыт производства битумной продукции из остаточных продуктов комбинированной установки гидрокрекинга гудрона АО «ТАИФ-НК»

The article is devoted to the use of residual products of combined thermal and hydrocracking of vacuum residue and vacuum gasoil into demanded marketable petroleum products - into bitumen products in accordance with Russianand international quality standards.

Comparative analysis of the effects of hydrogen and formic acid on the vacuum residue hydrocracking

The improvement of the existing technologies aimed at deeper processing of heavy oils and oil residues and development of new ones is an urgent task of modern oil refining. Experiments in a flow installation using a quartz reactor were performed to determine the formic acid decomposition pathway. The experiments showed that the formic acid decomposition over the Ni-Mo/Al2O3 catalyst predominantly yielded hydrogen and CO2. Therefore, in this study comparative experiments on the effects of hydrogen and formic acid on the vacuum residue hydrocracking in the presence of the Ni-Mo/Y-Al2O3 and Ni-Mo/Al2O3 catalysts were performed at 375–400 °C and 0.45 MPa pressure. The concentration of hydrogen or formic acid in argon was 10 vol%. The catalysts were prepared by impregnation of the corresponding supports with the aqueous solution obtained using nickel hydroxide, ammonium heptamolybdate and citric acid. Electron microscopy and XRD studies of the Ni-Mo/Y-Al2O3 and Ni-Mo/Al2O3 catalysts demonstrated that the active component in the studied catalysts was in a finely dispersed state. The size of Ni-Mo particles was 0.4–0.6 nm in the Ni-Mo/Y-Al2O3 catalyst and 0.3–0.6 nm in Ni-Mo/Al2O3. For both catalysts Ni-Mo/Y-Al2O3 and Ni-Mo/Al2O3 higher vacuum residue conversion to liquid products was observed in the presence of formic acid than in the presence of hydrogen. Hydrogen substitution for formic acid vapor during the vacuum residue hydrocracking also results in the lower sulfur content in the liquid reaction products. The use of formic acid as a hydrogen donor significantly simplifies the process hydrocracking.

Synthesis and performance of mesoporous iron oxide in vacuum residue slurry-phase hydrocracking

In order to develop a high-efficiency iron oxide catalyst for the slurry-phase hydrocracking of poor heavy oil, the mesoporous iron oxide was successfully synthesized by using the waste wood powder as a template, and the influence of alkali concentration in the resulting solution on crystal phase, morphology and pore structure of the synthesized samples was investigated. The crystal phase of the synthesized iron oxide transfers from α-Fe2O3 to γ-Fe2O3, and their crystal sizes gradually decrease with an increase of alkali concentration based on the XRD and HRTEM results. Additionally, the iron oxide with mesoporous structure, larger surface area and pore volume is obtained at the higher concentration of alkali in solution confirmed by N2 adsorption-desorption analysis. The assessment result of the iron oxide catalyst employed in the slurry-phase hydrocracking of vacuum residue (VR) illustrates that the yields of gasoline and diesel distillates obtained over Fe-O-B20, Fe-O-B24 and Fe-O-B30 catalysts are higher compared with those over Fe-O-B2 and Fe-O-B14 catalysts, it can be attributed that more exposure Fe active sites derived from their larger surface area and pore volume availably improve the catalyst hydrogenation activity, which can inhibit the over-cracking reaction of intermediate products and the condensation of polycyclic aromatic hydrocarbon in VR to enhance the yields of gasoline and diesel distillates.

Hydrocracking of vacuum residue in a slurry phase reactor: effect of reaction temperature and properties of feedstock

Abstract The slurry phase hydrocracking was carried out in a 150 kg/d pilot plant with a change of reaction temperature and different feedstocks including vacuum residue (VR), thermal cracking residue (TCR), 58% VR + 42% DOA (VRD) and 32% VR + 27% DOA + 41% TCR (VRDT). The results demonstrated that the conversions of residue and asphaltene, and hydrogen consumption had a linear relationship with the increment of reaction temperature. The TCR, VRD and VRDT with high content of asphaltene had the characteristic of higher asphaltene conversion and coke yield, but the coke yield was still low, and less than 1.3%. In addition, the removal rate of sulfur was much higher than that of nitrogen, while that of nickel and vanadium reach above 77 and 88%, respectively. The light liquid fraction product could further transform into high value-added chemical materials or clean transport fuel, and the heavy liquid fraction product could utilized as a very good raw material for high quality products as needle coke and carbon-based materials.

Beneficial effect of V on stability of dispersed MoS2 catalysts in slurry phase hydrocracking of vacuum residue: XAFS studies

The structure and the catalytic activity of the dispersed VxMo(1−x)S2catalysts were investigated for hydrocracking (HCK) of vacuum residue (VR) with the same amount of catalyst loading of 0.113 mmol as a metal basis at 693 K and 9.5 MPa H2. The catalysts were prepared in situ in the reaction using vanadium acetylacetonate and molybdenum hexacarbonyl as V and Mo precursors, respectively. Structural properties of the dispersed catalysts were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy and transmission electron microscopy, which confirmed the formation of a well-dispersed V-MoS2phase in size range 6–8 nm. Furthermore, it was demonstrated that the V-MoS2catalysts feature higher stability in the catalyst recycle test for the VR HCK in terms of H2 consumption rate (TOF) and asphaltene conversion in comparison to monometallic sulfides of V2S3 or MoS2.

Influence of ASA composition on its supported Mo catalyst performance for the slurry-phase hydrocracking of vacuum residue

To deeply illuminate the effect of ASA composition on its corresponding Mo catalyst properties and performance for the slurry-phase hydrocracking of vacuum residue, the amorphous silica-alumina (ASA) samples with the various ratios of Al to Si were successfully synthesized by a simple co-precipitation method, which have the different acid properties and pore structure, especially ASA-1 with lowest ratio of Al to Si owning the largest number of B acid sites and the highest volume of mesoporous. Additionally, the Mo catalyst supported on ASA-4 possesses the highest dispersion of MoS2 slabs and largest amount of Mo atoms located at the edge sites among all the catalyst, possibly due to the appropriate surface properties of ASA-4 derived from the ratio of Al to Si, it demonstrates that the most exposure Mo active sites are present on Mo/ASA-4 catalyst. The hydrocracking evaluation results show that the VR conversion over the different catalysts are similar, it may be ascribed to the variation of acid properties and pore structure insufficient to change VR cracking pathway because of the low catalyst dosage. Furthermore, the Mo/ASA-4 catalyst exhibits the higher yield of naphtha and middle distillate and inversely the lower yield of gas and coke in comparison with other catalysts, it should be attributed that the higher hydrogenation activity derived from the more exposure Mo active sites can efficiently restrain the over-cracking of the intermediate product and aggregation of the polycyclic aromatic hydrocarbon in the hydrocracking process.