Upgrading Of Heavy Crude Oil Research Articles

Intensification of the steam stimulation process using bimetallic oxide catalysts of MFe2O4 (M\u2009=\u2009Cu, Co, Ni) for in-situ upgrading and recovery of heavy oil

In this study, bimetallic catalysts based on transition metals CuFe2O4, CoFe2O4 and NiFe2O4 are proposed for catalyzing aquathermolysis reaction during steam-based EOR method to improve in-situ heavy oil upgrading. All upgrading experiments were carried out under a nitrogen atmosphere for 24 h in a 300-ml batch Parr reactor at 250 and 300 °C under high pressure 35 and 75 bar, respectively. To evaluate the catalytic performance of the bimetallic catalysts used, comprehensive studies of changes in the physical and chemical properties of the improved oils, including the viscosity, elemental composition and SARA fractions of oils before and after upgrading processes were used. Furthermore, individual SARA fractions were characterized in detail by Gas Chromatography (GC), High-Performance Liquid Chromatography (HPLC) and Carbon-13 Nuclear Magnetic Resonance (13C NMR), respectively. The results showed that bimetallic catalysts have high catalytic performance at 300 °C for the upgrading of heavy crude oil in viscosity reduction, increasing the amount of saturates (especially alkanes with low carbon number) as a result of thermal decompositions of high molecular weight compounds like resin and asphaltenes leading to their increasing. Furthermore, the upgrading performance is reflected in the improvement of the H/C ratio, the removal of sulfur and nitrogen through desulfurization and denitrogenation procedures, and the reduction in polyaromatic content, etc. CoFe2O4 gives the best performance. Generally, it can be concluded that, used bimetallic based catalysts can be considered as promising and potential additives improving in-situ upgrading and thermal conversion the heavy oils.

NiO based catalysts obtained “in-situ” for heavy crude oil upgrading: effect of NiO precursor on the catalytic cracking products composition

Heavy and super-heavy oils are characterized by a high content of resins and asphaltenes, which complicate the transportation and refining of oil and lead to an increase in the cost of refinery products. Currently, of particular interest are catalysts that are formed directly under the conditions of the process from precursors, which are various salts. In this work influence of NiO precursor on the heavy oil catalytic cracking products composition. The upgrading in all experiments was carried out at a temperature 450 °C for 80 min. The optimal catalyst content calculated to the NiO in experiments 2 and 3 was 0.5 wt. % of the feedstock weight. The ratio salt:ethanol in experiment 3 was 1:1 wt. The products of catalytic cracking were analyzed by SARA, GC, XRD and FT-IR spectrometry. The dissolution of Ni(NO3)2•6H2O in ethanol results in a decrease in the content of high molecular weight components and an increase in the yield of the fraction boiling up to 360 °C. A decrease of sulfur content in the course of heavy oil cracking is caused by both interactions of NiO formed over cracking with S-containing compounds of feedstock leading to formation of Ni9S8 and Ni0.96S and sulfur removal in form of gas.

Computational study of particle distribution development in a cold-flow laboratory scale downer reactor

The use of downer reactors (gas-solid co-current downward flow) in the Fluid Catalytic cracking (FCC) process for the upgrading of heavy crude oil into more valuable products has gradually become more common in the last decades. This kind of reactor is characterized by having homogeneous axial and radial flow structures, no back mixing, and shorter residence times as compared with the riser reactor type. Although downer reactors were introduced a long time ago, available information in literature about the multiphase hydrodynamic behavior at FCC industrial scale is scarce. Therefore, it is necessary to conduct experimental and computational studies to enhance the understanding of the hydrodynamics of two-phase co-current downward flow. The Computational Fluids Dynamics (CFD) software, Ansys Fluent, is used to study two-dimensional gas (air) and solid (catalyst particle) flow in a downer section of a cold-flow circulation fluidized bed (CFB) system at a laboratory scale. The implemented computational model is validated by comparing numerical results for solid velocity and volume fraction with measurements carried out on a CFB system using a fiber-optic probe laser velocimeter. According to numerical results obtained for different gas velocity and solid flux, flow development cannot only be estimated by considering solid axial velocity changes along the reactor; it is also necessary to take into account solid volume fraction axial variations as radial profiles can change even when velocity profiles are developed.

Molybdenum sulfide nanoparticles prepared using starch as capping agent. Redispersion and activity in Athabasca Bitumen hydrotreating

Nanoparticles of MoS3 were synthesized from (NH4)2MoS4 in acid media using water-soluble starch as a capping agent. X-Ray Diffraction patterns confirmed the formation of MoS3 while Transmission Electron Microscopy results showed the presence of nanoparticles with sizes of about 30−40 nm that were covered by the polymer. X-Ray Photoelectron spectroscopy analysis confirmed the formation of molybdenum sulfides. The MoS3 nanoparticles were thermally treated in CS2/H2 and converted to MoS2 nanoparticles which showed very low or no stacking of the slabs. The activity of the latter was assessed in the hydrodesulfurization of Vacuum Gas Oil (VGO) and upgrading of Athabasca bitumen. The solids that were prepared using starch exhibited better catalytic activity when compared to commercial MoS2 nanoparticles (Hydrotreating of Vacuum Gasoil) and a NiMo/Al2O3 supported catalyst (upgrading of bitumen), and the stacking of the layers did not increase after reaction. This opens up the possibility of using the facile method of preparation here developed for the application of nanoparticles in a slurry process for heavy crude oil upgrading.

Fe/HZSM-5 catalytic pyrolysis cellulose as hydrogen donor for the upgrading of heavy crude oil by one-pot process

The combine utilization of traditional fossil sources and biomass energy is a new idea with great potential. In this study, established the heavy crude oil upgrading system combine with cellulose, and the hydrogen supply effect of catalytic pyrolysis of cellulose was discussed. Fe/HZSM-5 increased the pyrolysis of cellulose, resulting in a bio-oil yield of up to 84%, and the potential components that employed as hydrogen donors (such as alcohols, aromatics, aliphatic-hydrocarbons) are increased to varying degrees, which ensures more efficient in heavy crude oil upgrading. The heavy crude oil viscosity decreased from 10,460 mpa·s to 2083 mpa·s after cellulose and heavy crude oil upgrading catalyzed by 5%Fe/HZSM-5 at 350 °C. A series of qualitative evaluations from the perspective of hydrogen supply, including FT-IR, Elemental analysis, SARA and 1HNMR, found significant improvements in the quality of the heavy crude oil.

A novel direct method in one-step for catalytic heavy crude oil upgrading using iron oxide nanoparticles

We proposed a direct in situ synthesis method for iron oxide nanoparticles (NPs) along with catalytic erformance upgrading of heavy crude oil (HCO). Our method compares the upgrading of a HCO where other iron oxide nanoparticles were synthesized by a traditional thermal decomposition method of organometallic compounds in the presence of stabilizing agents and solvents of high boiling points. Furthermore, the in situ nanoparticles were extensively characterized by XRD, Mössbauer spectroscopy and TEM microscopy which confirmed the presence of magnetite and akaganeite phases, with an average diameter of 20−43 nm. Nanoparticles by thermal decomposition method were investigated by XRD, UHR-FE-SEM and HRTEM and showed the formation of magnetite nanoparticles with an average diameter of 6.7 ± 1.4 nm. Subsequently, the nanoparticles were evaluated in a batch reactor using HCO from the Golden Lane of Mexico at 44.1 bar (initial H2 pressure) and 380 °C, for 1 h at 500 rpm. It was observed that, even under hydrogen limited conditions, there are better physicochemical properties in terms of viscosity, API gravity and heavy fractions decrease, for example, the residue conversion was about 20 % and the kinetic model was adjusted to a five lump model. The formation of the iron sulfide phase (FeS) was detected during the analysis of the spent catalyst.

Catalytic Upgrading of Heavy Oil using FCC Equilibrated Catalyst

Heavy crude oil is an important unconventional hydrocarbon resources that can be upgraded to useful petroleum products. However, heavy oil has some challenges due to its high viscosity, low mobility coupled with its low API gravity, these features make processing and transportation of heavy oil quite challenging. Consequently, there is need to upgrade heavy oil using suitable technique and appropriate catalyst. In this study, an equilibrated FCC catalyst (E-CAT) was sourced from a refinery, characterized using XRD, XRF and FT-IR techniques and tested in upgrading heavy crude oil. In a preliminary work, heavy gas oil (HGO) and vacuum gas oil (VGO) were used as model oils. They were cracked in a high pressure-high temperature batch reactor at varying temperatures of 350, 400 and 450oC, initial pressure of 1MPa and catalyst-to-oil ratio of 0.01 for the catalytic reaction. Parameters studied include viscosity reduction and change in structural composition of the model oils before and after upgrading using FT-IR technique. Results of VGO upgrade showed viscosity reduction of 3.5, 10 and 32% after thermal upgrade at 350,400, 450oC and 10, 15 and 42% after catalyst addition at the temperatures respectively. The HGO upgrading result showed viscosity reduction of 4, 7 and 24% after thermal upgrade at 350, 400 and 450 oC respectively and 6, 13 and 33% viscosity reduction after catalyst addition correspondingly. FT-IR results suggest the formation of saturated hydrocarbons an indication of the formation of valuable products after upgrading reactions with a better results recorded after catalyst addition. Results from the experimental investigation showed that the E-Cat has the potential to be used in heavy crude oil upgrading

New approach to unsupported ReS2 nanorod catalyst for upgrading of heavy crude oil using methane as hydrogen source

Highly active ReS2 nanocatalysts were prepared by CVD method and characterized by XRD, BET -BJH, Raman spectroscopy, XPS, TPR, NH3-TPD, SEM, and HRTEM techniques. Catalytic activities were used in upgrading heavy crude oil using methane as hydrogen source. The results showed a significant increase in API and decrease in sulfur and nitrogen content of crude oil. RSM technique was used to investigate the interactive effects of temperature (200–400 °C), pressure (20–40 bar) and dosage of nanocatalyst (0.5–2 wt. %) on the performance of HDS reaction. The results represent that the maximum predicted HDS activity (74.375%) was estimated under the optimal conditions (400 °C, 20 bars, and 2 wt % of nanocatalyst). Also, the effect of reaction temperature, pressure and dosage of ReS2 nanorods catalyst on HDN of heavy crude oil was investigated and highest efficiency in the HDN process (93%) occurred at 400 °C and 40 bar using 2 wt % ReS2.

Parametric study of particles homogenization in cold-flow riser reactors

Fluid Catalytic cracking (FCC) process are frequently used for the upgrading of heavy crude oil into more valuable products. Traditionally, the FCC process occurs in a riser reactor, where both vaporised hydrocarbon feed-stock and solid catalyst flow in the direction against gravity. This kind of reactor presents heterogeneous flow distributions that affect the axial and radial flow structures, as well as the product quality. To understand the effect of operational variables over riser flow distribution, a numerical study of the two-phase cold-flow in the pre-acceleration zone of a riser reactor fed with catalyst particles used in this kind of reactors is presented in this work considering a two-dimensional model. The Computational Fluids Dynamics (CFD) software ANSYS® Fluent® is used to study two-dimensional gas (air) and solid (catalyst particle) flow in a riser section of a cold-flow Circulation Fluidized Bed (CFB) system under different flow inlet conditions (i.e., either for the gas and solid flux), as well the particle diameter size. An Eulerian-Eulerian approach, including the turbulence ( κ − ε model) and the Kinetic Theory of Granular Flow (KTGF) models, are solved for the gas phase and the solid particles treated as a dispersed phase. The implemented computational model is validated by comparing numerical results for solid velocity and volume fraction distribution to values reported by peers. As expected, a higher concentration towards the axis of the reactor is obtained for the solid volume fraction values. The R N I index estimated for gas velocities of 3 m/s and 4 m/s are significantly lower than the others, indicating that as the inlet gas velocity is reduced, a more homogeneous profile is obtained. Finally, the numerical results obtained shown closer to the experimental data used for the validation as the steady-state is attained.

Microstructural Investigation of Coke Deposition in Pelleted Catalyst during Downhole Catalytic Upgrading of Heavy Crude Oil Using Porosimetry and X-ray Computed Tomography

Catalyst pore evolution due to coke and metals (e.g., Ni, V, etc.) deposition from heavy oil catalytic upgrading is studied using nitrogen adsorption–desorption, mercury porosimetry, X-ray computed tomography and Scanning electron microscope (SEM) techniques. These techniques probe the impact of coking on the global pore size distribution and the pore-scale connectivity of pores of different sizes. 24wt% coked NiMo/Al2O3 catalyst was studied. Coke deposition caused active site coverage and pore-mouth blockage making the core pore network inaccessible to reactants as reflected in the nearly loss of total surface area and pore volume observed from porosimetry, while the x-ray computed tomography image shows scanty coke deposits within the microstructure. The SEM image confirmed that pore-mouth blockage due to large coke deposition in the early hours of the upgrading reactions at the outer layer of the catalyst pellets is the major cause of deactivation. The spent catalyst experienced more than 90% drop in surface area with coke deposition on the outer layer of the catalyst far higher than in the centre. Therefore, one of the ways to enhance intra-particle diffusion and limit the impact of coke deposition on the outer layer of the catalyst is either to use nano-catalyst or engineered pore sizes.

Upgrading of heavy crude oil by thermal and catalytic cracking in the presence of NiCr/WC catalyst

The heavy crude oil of the Mordovo-Karmal deposit was cracked in the presence of NiCr/WC catalyst. The catalytic upgrading heavy crude oil was carried out in the batch reactor at 450 °C, catalyst content in the range of 0.01‒0.20 wt%, and 100 min of residence time. It is shown that the cracking in the presence of a catalyst results in the formation of a light ‘synthetic’ oil. The viscosity of the liquid products of catalytic cracking decreases by an order of magnitude. The content of the fractions boiling up to 360 °C increases to 78 wt%, while the content of resins, asphaltenes, and sulfur decreases.

Saturates and aromatics characterization in heavy crude oil upgrading using Ni–Co/γ-Al2O3 catalysts

The saturates and aromatic constituents of the resulting light crude oil during catalytic and thermal upgrading of Omani heavy crude oil were further characterized to elucidate the crucial role of Ni–Co/γ-Al2O3 catalyst and gas media. GC-MS analysis confirms that water-gas shift reaction (WGSR) promotes a type of hydrogenation reaction resulting in higher saturates contents of the upgraded oil in nitrogen media. In a bid to buttress the relevance of the catalyst, C7–C30 homologous series results show that the quantities of marketable components in the crude oil were higher with catalytic upgrading than thermal cracking.

NiFe2O4 nanocatalyst for heavy crude oil upgrading in low hydrogen/feedstock ratio

In this work, we probe the effect of NiFe2O4 nanoparticles (NPs) as catalysts in heavy crude oil upgrading in low hydrogen/feedstock ratio, that can occur in places where the conditions cannot be controlled, such as inside oil reservoir. The NPs were synthesized by the thermal decomposition method of metal precursors. In order to obtain the NPs, the decomposition of nickel and iron acetylacetonate was done in presence of oleic acid and oleylamine, which worked as solvents, and stabilizing and reducing agents (the solution was heated to 200 °C for 2 h and then, heated to reflux to 300 °C for 30 min).The produced NPs were characterized by UHR-FE-SEM and spherical aberration-corrected STEM. These techniques revealed the formation of nanoparticles with an average size of 10 ± 1.7 nm and the determination of the crystalline arrangement of the nanomaterials. Additionally, XRD confirmed that nanoparticles corresponded to the crystallographic phase (NiFe2O4). The experiments were performed in a batch reactor at an initial 100% H2 pressure of 45 Kgf. cm−2 and 380 °C, during 1 h at 500 rpm. NiFe2O4 NPs increased the upgrading of heavy oil, evaluated by viscosity, API gravity, sulfur and nitrogen removal, and simulated distillation analysis; residue conversion was approximately 28% and sulfur removal reached values of up to 20%. The analysis of spent catalyst by XPS showed that the iron sulfide phase (FeS) was formed.

Preparation of disk-like α-Fe2O3 nanoparticles and their catalytic effect on extra heavy crude oil upgrading

In this paper, disk-like α-Fe2O3 nanoparticles were synthesized by one-step via an n-octyl alcohol-mediated self-assembly process and were subsequently used as the catalyst for the updating of heavy crude oil. The characterization results show that the diameter of the as-prepared α-Fe2O3 disks is in the range of 150–200 nm and the nanoparticles have a hematite structure with [1 1 0] preferred orientation. The catalyst strongly acts on the asphaltene and causes its lower S content and N content, lower aromaticity and aromatic condensation, and higher branchiness index. Adding tetralin causes the increment of aromatics content, the decrease of resin, and more molecules containing aromatic moieties bearing 2 and 3 rings. The viscosity of the Shengli extra heavy oil reduced substantially from 161180 mPa∙s to 45882 mPa∙s (50 °C) through the combination of the α-Fe2O3 nanoparticles and tetralin (a hydrogen donor).

Biodegradation of long chain alkanes in halophilic conditions by Alcanivorax sp. strain Est-02 isolated from saline soil

In this study, through a multistep enrichment and isolation procedure, a halophilic bacterial strain was isolated from unpolluted saline soil, which was able to effectively and preferentially degrade long chain alkanes (especially tetracosane and octacosane). The strain was identified by 16S rRNA gene sequence as an Alcanivorax sp. The growth of strain Est-02 was optimized at the presence of tetracosane in different NaCl concentrations, temperatures, and pH. The consumption of different heavy alkanes was also investigated. Optimal culture conditions of the strain were determined to be as follows: 10% NaCl, temperature 25-35°C and pH 7. Alcanivorax sp. strain Est-02 was able to use a wide range of aliphatic substrates ranging from C14 to C28 with clear tendency to utilize heavy chain hydrocarbons of C24 and C28. During growth on a mixture of alkanes (C14-C28), the strain consumed 60% and 65% of tetracosane and octacosane, respectively, while only about 40% of the lower chain alkanes were degraded. This unique ability of the strain Est-02 in efficient and selective biodegradation of long chain hydrocarbons could be further exploited for remediation of wax and heavy oil contaminated soils or upgrading of heavy crude oils. Comparison of the sequence of alkane hydroxylase gene (alkB) of strain Est-02 with previously reported sequences for Alcanivorax spp. and other hydrocarbon degraders, showed a remarkable phylogenetic distance between the sequence alkB of Est-02 and other alkane-degrading bacteria.

Catalytic upgrading of heavy oil using NiCo/γ-Al2O3 catalyst: Effect of initial atmosphere and water-gas shift reaction

Ni-Co/γ-alumina catalyst was prepared and tested in upgrading of heavy crude oil. The parameter studied was the type of the pressurising gas and especially its effect on the water-gas shift reaction on the upgrading. The preliminary results suggested that a combination of the cracking reaction and the original water-in-oil which triggered a low temperature water-gas shift reaction generated hydrogen in-situ for the hydrogenation reaction. To further explore this, four major experimental runs were conducted; amongst which two were without catalysts and reactor inner liner in hydrogen and nitrogen environments, two were catalytically driven with and without a liner. The experimental conditions were 380 °C, 32 bar and residence time of 2 h with a catalyst/oil ratio of 0.01. The results show that API gravity, Hydrogen/Carbon ratio and light oil yields were slightly higher for the reaction in nitrogen atmosphere without liner as compared to hydrogen with liner– 15.8°, 0.138, and 40.2 g respectively for the latter with 18.2°, 0.177, and 45 g for the former. The catalytic reaction in hydrogen environment however; produced no coke as against the 0.2 wt% coke recorded with nitrogen. Meanwhile, the reduction in sulphur content and viscosity of the nitrogen experiment were higher compared to that of hydrogen.

Thermocatalytic upgrading of heavy oil by iron oxides nanoparticles synthesized by oil-soluble precursors

Thermocatalytic upgrading of heavy crude oil at reservoir temperature and pressure has been studied. The objective of the present work was to investigate the efficiency of the compounds based on iron (iron carbonyls, iron oxide, metallic iron) on thermocatalytic upgrading process of heavy crude oil at reservoir temperature and pressure (5.0 MPa and up to 523.15 K). The viscosity reducing was used as the main parameter for determination of the efficiency of thermocatalytic upgrading. The effect of structure of the catalyst precursor on the composition of SARA fractions after thermal catalytic upgrading of crude oil was analyzed. A destruction of mainly resin fraction was found to occur during thermocatalytic upgrading of heavy crude oil. The composition and structure of catalysts after crude oil upgrading were determined by the X-powder diffraction and SEM methods. An impact of catalyst (Fe3O4) particle size on the efficiency of crude oil thermocatalytic upgrading process was revealed.

The synergistic effect between supercritical water and redox properties of iron oxide nanoparticles during in-situ catalytic upgrading of heavy oil with formic acid. Isotopic study

Catalytic treatment in water medium under high-pressure condition could be an attractive technology for clean upgrading of heavy crude oils and residua with effective heteroatom removal to meet the qualified liquid transportation fuels. By applying isotope labeling technique, an experimental study has been reported here to gain insights in the catalytic performance of iron/iron oxide nanocatalysts for upgrading vacuum residue (VR) in supercritical water (SCW) and formic acid (FA) solution. The results show that the hematite iron oxide nanoparticles with a higher oxidation state (Fe3+) are more effective in the oxidative removal of heteroatoms (sulfur, nitrogen) and in the reduction of heavy constituents (e.g., asphaltene) to light oil; while, magnetite (Fe3+/Fe2+) is superior in the hydrogenation of light hydrocarbons. Contrary to the upgrading in the steam atmosphere, SCW has strong influence on the recovery of converted iron oxide to the higher oxidation state (Fe2+ → Fe3+), which can recompense the lattice oxygen loss of the catalyst during the cracking process. The advantage of heavy oil upgrading by using iron oxide nanoparticles in SCW + FA solution is that water pressure can enhance the capability of catalyst in providing the oxygen for the oxidative cracking as well as the effective hydrogenation of heavy oil by active hydrogen from the water-gas shift reaction.

How effective is Refinery Regenerated Catalyst for Downhole Catalytic Upgrading of Heavy Crude Oil?

How effective is Refinery Regenerated Catalyst for Downhole Catalytic Upgrading of Heavy Crude Oil?

Experimental Study and Economic Analysis of Heavy Oil Partial Upgrading by Solvent Deasphalting–Hydrotreating

Technical and economical evaluation was carried out for upgrading of heavy crude oil through a combined scheme integrated by deasphalting and hydrotreating. Deasphalted oil was obtained at 60°C of temperature, 25 kgf/cm2 of pressure, 5:1 solvent/oil ratio and 1 hour of residence time, using n-heptane as solvent. Deasphalted oil product was upgraded by means of hydrotreating at low severity reaction conditions: 360°C of temperature, 60 kgf/cm2 of pressure and 4 hours of reaction time. The feasibility analysis demonstrated that the upgrading scheme is an appropriate option for producing transportable oil, that yields a benefit of 3.42 USD/Bbl.