The potassium storage performance of carbon nanosheets derived from heavy oils

As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the relationship between heavy oil composition and potassium storage performance remains unclear.Using heavy oils containing distinct chemical groups as the carbon source,namely fluid catalytic cracking slurry(FCCS),petroleum asphalt(PA)and deoiled asphalt(DOA),three carbon nanosheets(CNS)were prepared through a molten salt method,and used as the anodes for PIBs.The composition of the heavy oil determines the lamellar thicknesses,sp3-C/sp2-C ratio and defect concentration,thereby affecting the potassium storage performance.The high content of aromatic hydrocarbons and moderate amount of heavy component moieties in FCCS produce carbon nanosheets(CNS-FCCS)that have a smaller layer thickness,larger interlayer spacing(0.372 nm),and increased number of folds than in CNS derived from the other three precursors.These features give it faster charge/ion transfer,more potassium storage sites and better reaction kinetics.CNS-FCCS has a remarkable K^(+)storage capacity(248.7 mAh g^(-1) after 100 cycles at 0.1 A g^(-1)),long cycle lifespan(190.8 mAh g^(-1) after 800 cycles at 1.0 A g^(-1))and excellent rate capability,ranking it among the best materials for this application.This work sheds light on the influence of heavy oil composition on carbon structure and electrochemical performance,and provides guidance for the design and development of advanced heavy oil-derived carbon electrodes for PIBs.

Rapid accuracy determining DNA purity and concentration in heavy oils by spectrophotometry methods

DNA analysis is the core of biotechnology applied in petroleum resources and engineering. Traditionally accurate determination of DNA purity and concentration by spectrometer is the first and critical step for downstream molecular biology research. In this study, three different spectrophotometry methods, BPM, NDTT and NPMTTZ were compared for their performance in determining DNA concentration and purity in 32 oil samples, and molecule methods like quantitative real-time PCR (qPCR) and high-throughput sequence were also performed to help assess the accuracy of the three methods in determining DNA concentration and purity. For ordinary heavy oil (OHO), extra heavy oil (EHO) and super heavy oil (SHO), the characteristics of high viscosity (η), density (ρ) and resin plus asphaltene content will affect the DNA extraction and UV determination. The DNA concentration was decreased as density increased: OHO (11.46 ± 18.34 ng/μL), EHO (6.68 ± 9.67 ng/μL) and SHO (6.20 ± 7.83 ng/μL), and the DNA purity was on the reverse: OHO (1.31 ± 0.27), EHO (1.54 ± 0.20), and SHO (1.83 ± 0.32). The results suggest that spectrophotometry such as BPM and NPMTTZ are qualitatively favorite methods as the quick non-consumable methods in determining DNA concentration and purity of medium oil and heavy oil.

Direct Fingerprinting Polycyclic Aromatic Hydrocarbons in Heavy Oils by PY-GC/MS and Its Application to Hydrotreating Processes

An efficient analytical method combining pyrolysis and capillary GC/MS has been developed for determination and quantitation of targeted polycyclic aromatic hydrocarbons.The limit of detection ranged from 0.29 μg/g to 43.46 μg/g,and repeatability values were between 0.1% and 8.2% for blank spiked samples and between 0.1 % and 9.8% for real samples of heavy oils.Through application of the proposed method in hydrotreating processes,it has been found out that heavy oils before and after the specified hydroprocessing treatment exhibited a diverse PAHs distribution which might be determined by the discrepancy in their intrinsic contents and hydrogenation reactivity.Furthermore,the hydrogenation reactivity of different polycyclic aromatic hydrocarbons was further investigated and discovered to be more interrelated to molecular structure and rings alignment or conjugation mode.

Geochemical Characterization and Origin of High-Sulfur,Heavy Oils in Jiyang Sub-Basin,East China

High-sulfur,heavy petroleum is widely occurring in the Tertiary lacustrine Jiyang sub-basin, Bohai Bay Basin.They are differentiated into two families based on the bulk properties and biomarker compositions.Family 1 is characterized by high resins（40%-71%）and sulfur（2%-4%）,and low wax （l%-6%）,with n-alkanes removed by biodegradation,whereas family 2 is characterized by extremely abundant sulfur（3%-10%）,and high asphaltenes（7%-31%）and wax（2%-19%）,with no evidence of microbial attack.The oils of family 1 are distributed in the reservoir,lower than 1500 m throughout the sub-basin.Biomarker assemblages,such as low pristane/phytane ratios（1 Pr/Ph）and a high abundance of carotane,gammacerane,and dinosterane,suggest that they are derived from the calcareous mudstones and shales among the stratified,saline Es_4~u unit,in addition to the in situ biodegradation-concentrated sulfur content.However,the oils of family 2 are identified only in the western Zhanhua and eastern Chezhen depressions,with a depth deeper than 1700 m.Physical properties,together with biomarker ratios,including even-numbered n-alkanes,1 Pr/Ph,trace diasteranes,higher C35 homohopanes,and abundant dibenzothiophene series,with1 dibenzothiophene/phenanthrene,indicate an origin from carbonate source rocks.The X-ray diffraction analysis showed that the carbonate source rock is limited in the Es_4~u unit of the Bonan sag,which is different from most other source rocks in the same horizon.It is suggested that the high-sulfur,heavy oils are generated at the early stage of the oil window.Bacterial sulfate reduction might be responsible for the occurrence of sulfur species in the high-sulfur,heavy oils,while heavy biodegradation will enhance sulfur concentrations.

Origin of Shallow Jurassic Heavy Oils in the Northwestern Margin of the Junggar Basin,NW China:Constraints from Molecular,Isotopic and Elemental Geochemistry

Oil group separation,gas chromatography-mass spectrometry analysis of saturated hydrocarbons,carbon isotope analysis of fractions and tests on trace elements were all carried out to determine the origin of shallow Jurassic heavy oils in the northwestern margin of the Junggar Basin,northwestern China.Results showed that all the crude oils had been subjected to different degrees of biodegradation,on an order ranging from PM 6 to 9,which yielded many unresolved complex mixtures(UCM)and formed a huge spike in the mass chromatogram(M/Z=85).Two heavy oils from the Karamay area underwent slight biodegradation,characterized by the consistent ratios of biomarker parameters.C_(21)/C_(23)and C_(23)/H of the two samples were 0.81 and 0.85,while G/H,C_(27)/C_(29)and C_(28)/C_(29)were 0.38 and 0.40,0.16 and 0.27,0.87 and 0.86,respectively.The isomerization parameters of terpane and steranes were 0.50-0.53,and 0.48-0.49,respectively.The above geochemical indices indicated that the crude oils in the study area were in the marginally mature stage.The parent materials were a mixture,consisting of bacteria,algae and some higher plants,formed under reducing depositional conditions,which is in agreement with the source rocks of the Fengcheng Formation in the Mahu depression.The carbon isotopic compositions of saturated hydrocarbon,aromatic hydrocarbon,NSO and asphaltene were−31‰−to−30.3‰,−29.5‰to−29.03‰,−29.4‰to−28.78‰and−28.62‰to−28.61‰,respectively.These findings are in agreement with the light carbon isotope of kerogen from the lower Permian Fengcheng Formation.Furthermore,V/Ni and Cr/Mo of all the crude oils were 0.01 to 0.032,0.837 to 10.649,which is in good agreement with the ratios of the corresponding elements of the extracts from the Fengcheng Fm.carbonate source rock.As a result,a two-stage formation model was established:(1)the oil generated from the carbonate source rocks of the Fengcheng Formation migrated to the Carboniferous,Permian and Triassic traps during the Late Triassic,forming the primary oil reservoirs;(2)during the Late Jurassic period,the intense tectonic activity of Yanshan Episode II resulted in the readjustment of early deep primary reservoirs,the escaped oils gradually migrating to the shallow Jurassic reservoir through cross-cutting faults,unconformities and sand body layers.The oils then finally formed secondary heavy oil reservoirs,due to long-term biodegradation in the later stage.Therefore,joint methods of organic,isotopic and element geochemistry should be extensively applied in order to confirm the source of biodegradation oils.

Investigation on the biodegradation levels of super heavy oils by parameter-striping method and refined Manco scale: a case study from the Chepaizi Uplift of Junggar Basin

The Carboniferous volcanic reservoir in the Chepaizi Uplift became an exploration hot target in recent years for its substantial amount of oils discovered. However, most of the Carboniferous heavy oils were biodegraded to PM7 or higher with orders of magnitude variation in oil viscosities. Two oil groups (I and II) exactly corresponding to the western and eastern Chepaizi Uplift were distinguished according to their source diagnose. Furthermore, three oil families (II1, II2 and II3), with the biodegradation level of PM7, PM8–8+, PM9+, respectively, were classified based on molecular compositions and parameter-stripping method of strongly bioresistant parameters. Allowing for this extremely high biodegradation case, more biodegradation refractory compound class were added to establish a refined Manco scale to quantitatively evaluate the biodegradation extent. Refined Manco number (RMN2) positively correlated with the oil density, NSO contents, and absolute concentrations of diasteranes and gammacerane, negatively correlated with the absolute concentrations of diahopane, summed tricyclic terpanes and pentacyclic terpanes. This refined scale showed higher resolution than the PM one to differentiate the biodegradation extent of Carboniferous heavy oils from the Chepaizi Uplift, especially those with same PM values but different oil viscosities.

The mechanisms of thermal solidification agent promoting steam diversion in heavy oil reservoirs

At high cycles of steam huff&puff,oil distribution in reservoirs becomes stronger heterogeneity due to steam channeling.Thermal solidification agent can be used to solve this problem.Its solution is a lowviscosity liquid at normal temperature,but it can be solidified above 80℃.The plugging degree is up to 99%at 250℃.The sweep efficiency reaches 59.2%,which is 7.3%higher than pure steam injection.In addition,simultaneous injection of viscosity reducer and/or nitrogen foams can further enhance oil recovery.The mechanism of this technology depends on its strong plugging ability,which changes the flowing pattern of steam to effectively mobilize remaining oil.Viscosity reducer and nitrogen foams further expand the sweep range and extends the effective period.Therefore,thermal solidification agent can plug steam channeling paths and adjust steam flowing direction to significantly enhance oil recovery at high cycles of steam huff&puff.

Probing the interaction between asphaltene-wax and its effects on the crystallization behavior of waxes in heavy oil via molecular dynamics simulation

High content of asphaltenes and waxes leads to the high pour point and the poor flowability of heavy oil,which is adverse to its efficient development and its transportation in pipe.Understanding the interaction mechanism between asphaltene-wax is crucial to solve these problems,but it is still unclear.In this paper,molecular dynamics simulation was used to investigate the interaction between asphaltenewax and its effects on the crystallization behavior of waxes in heavy oil.Results show that molecules in pure wax are arranged in a paralleled geometry.But wax molecules in heavy oil,which are close to the surface of asphaltene aggregates,are bent and arranged irregularly.When the mass fraction of asphaltenes in asphaltene-wax system(ω_(asp))is 0-25 wt%,the attraction among wax molecules decreases and the bend degree of wax molecules increases with the increase ofω_(asp).Theω_(asp)increases from 0 to 25 wt%,and the attraction between asphaltene-wax is stronger than that among waxes.This causes that the wax precipitation point changes from 353 to 333 K.While theω_(asp)increases to 50 wt%,wax molecules are more dispersed owing to the steric hindrance of asphaltene aggregates,and the interaction among wax molecules transforms from attraction to repulsion.It causes that the ordered crystal structure of waxes can't be formed at normal temperature.Simultaneously,the asphaltene,with the higher molecular weight or the more hetero atoms,has more obvious inhibition to the formation of wax crystals.Besides,resins also have an obvious inhibition on the wax crystal due to the formation of asphalteneresin aggregates with a larger radius.Our results reveal the interaction mechanism between asphaltene-wax,and provide useful guidelines for the development of heavy oil.

Influence of pore structure heterogeneity on channeling channels during hot water flooding in heavy oil reservoir based on CT scanning

Hot water flooding is an effective way to develop heavy oil reservoirs.However,local channeling channels may form,possibly leading to a low thermal utilization efficiency and high water cut in the reservoir.The pore structure heterogeneity is an important factor in forming these channels.This study proposes a method that mixes quartz sand with different particle sizes to prepare weakly heterogeneous and strongly heterogeneous models through which hot water flooding experiments are conducted.During the experiments,computer tomography(CT)scanning identifies the pore structure and micro remaining oil saturation distribution to analyze the influence of the pore structure heterogeneity on the channeling channels.The oil saturation reduction and average pore size are divided into three levels to quantitatively describe the relationship between the channeling channel distribution and pore structure heterogeneity.The zone where oil saturation reduction exceeds 20%is defined as a channeling channel.The scanning area is divided into 180 equally sized zones based on the CT scanning images,and threedimensional(3D)distributions of the channeling channels are developed.Four micro remaining oil distribution patterns are proposed,and the morphology characteristics of micro remaining oil inside and outside the channeling channels are analyzed.The results show that hot water flooding is more balanced in the weakly heterogeneous model,and the oil saturation decreases by more than 20%in most zones without narrow channeling channels forming.In the strongly heterogeneous model,hot water flooding is unbalanced,and three narrow channeling channels of different lengths form.In the weakly heterogeneous model,the oil saturation reduction is greater in zones with larger pores.The distribution range of the average pore size is larger in the strongly heterogeneous model.The network remaining oil inside the channeling channels is less than outside the channeling channels,and the hot water converts the network remaining oil into cluster,film,and droplet remaining oil.

Catalytic Performance of Aquathermolysis and Viscosity Reduction of Heavy Oil over a WO_(3)/ZrO_(2) Solid Acid

Tungstated zirconia(WO_(3)/ZrO_(2))solid acid catalysts with different WO_(3) contents were prepared by a hydrothermal method and then used in the catalytic aquathermolysis of heavy oil from Xinjiang.The WO_(3)/ZrO_(2) solid acid catalyst was characterized by a range of characterization methods,including X-ray diffraction,NH3-temperature programmed desorption,and pyridine infrared spectroscopy.The WO_(3) content of the WO_(3)/ZrO_(2) catalysts had an important impact on the structure and property of the catalysts.When the WO_(3) mass fraction was 20%,it facilitated the formation of tetragonal zirconia,thereby enhancing the creation of robust acidic sites.Acidity is considered to have a strong impact on the catalytic performance of the aquathermolysis of heavy oil.When the catalyst containing 20%WO_(3) was used to catalyze the aquathermolysis of heavy oil under conditions of 14.5 MPa,340℃,and 24 h,the viscosity of heavy oil decreased from 47266 to 5398 mPa·s and the viscosity reduction rate reached 88.6%.The physicochemical properties of heavy oil before and after the aquathermolysis were analyzed using a saturates,aromatics,resins,and asphaltenes analysis,gas chromatography,elemental analysis,densimeter etc.After the aquathermolysis,the saturate and aromatic contents significantly increased from 43.3%to 48.35%and 19.47%to 21.88%,respectively,with large reductions in the content of resin and asphaltene from 28.22%to 25.06%and 5.36%to 2.03%,respectively.The sulfur and nitrogen contents,and the density of the oil were significantly decreased.These factors were likely the main reasons for promoting the viscosity reduction of heavy oil during the aquathermolysis over the WO_(3)/ZrO_(2) solid acid catalysts.

An Integrated Optimization Method for CO_(2) Pre-Injection during Hydraulic Fracturing in Heavy Oil Reservoirs

CO_(2) pre-injection during hydraulic fracturing is an important method for the development of medium to deep heavy oil reservoirs.It reduces the interfacial tension and viscosity of crude oil,enhances its flowability,maintains reservoir pressure,and increases reservoir drainage capacity.Taking the Badaowan Formation as an example,in this study a detailed three-dimensional geomechanical model based on static data from well logging interpretations is elaborated,which can take into account both vertical and horizontal geological variations and mechanical characteristics.A comprehensive analysis of the impact of key construction parameters on Pre-CO_(2) based fracturing(such as cluster spacing and injection volume),is therefore conducted.Thereafter,using optimized construction parameters,a non-structured grid for dynamic development prediction is introduced,and the capacity variations of different production scenarios are assessed.On the basis of the simulation results,reasonable fracturing parameters are finally determined,including cluster spacing,fracturing fluid volume,proppant concentration,and well spacing.

A Real-time Prediction System for Molecular-level Information of Heavy Oil Based on Machine Learning

Acquiring accurate molecular-level information about petroleum is crucial for refining and chemical enterprises to implement the“selection of the optimal processing route”strategy.With the development of data prediction systems represented by machine learning,it has become possible for real-time prediction systems of petroleum fraction molecular information to replace analyses such as gas chromatography and mass spectrometry.However,the biggest difficulty lies in acquiring the data required for training the neural network.To address these issues,this work proposes an innovative method that utilizes the Aspen HYSYS and full two-dimensional gas chromatography-time-of-flight mass spectrometry to establish a comprehensive training database.Subsequently,a deep neural network prediction model is developed for heavy distillate oil to predict its composition in terms of molecular structure.After training,the model accurately predicts the molecular composition of catalytically cracked raw oil in a refinery.The validation and test sets exhibit R2 values of 0.99769 and 0.99807,respectively,and the average relative error of molecular composition prediction for raw materials of the catalytic cracking unit is less than 7%.Finally,the SHAP(SHapley Additive ExPlanation)interpretation method is used to disclose the relationship among different variables by performing global and local weight comparisons and correlation analyses.

FCC Study of Canadian Heavy Gas Oils—Comparisons of Product Yields and Qualities between Reactors

Several series of cracking tests in a comprehensive study were conducted on separate occasions involving all or parts of ten Canadian vacuum gas oils (VGOs) and two catalysts with bottoms-cracking or octane-barrel capability. VGOs were cracked in fixed- and/or fluid-bed microactivity test (MAT) units, in an Advanced Cracking Evaluation (ACE) unit, and in a modified ARCO riser reactor. Individual yields of gas, liquid, and coke from the MATs at 55, 65, 70, and 81 wt% conversion levels were compared with their respective pilot plant data. Good linear correlations could be established between MAT and riser yields except for liquefied petroleum gas (LPG) and light cycle oil (LCO). At a given conversion, correlations existed among the fixed- and fluid-bed MAT units and the ACE for each product yield. Liquid products from the fixed or fluid-bed MAT were analyzed for hydrocarbon types, sulfur, nitrogen and density, most of which showed good agreement with those obtained from the riser study. When cracking Canadian oil-sands-derived VGOs, the bottoms-cracking catalyst containing a large-pore active matrix was found to be more suitable than the octane-barrel catalyst with smaller pores to produce higher yields of valuable distillates, but with less superior qualities (in terms of sulfur and nitrogen contents). The advantages of hydrotreating some poor feeds to improve product yields and qualities were demonstrated and discussed.

Formation mechanism of condensates, waxy and heavy oils in the southern margin of Junggar Basin, NW China

It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity and various chemical features.The central part of southern margin of Junggar Basin, NW China is such an example where there are condensates, light oils, normal density oils, heavy crude oils and natural gases. The formation mechanism of condensates has been seriously debated for long time;however, no study has integrated it with genetic types of waxy and heavy oils. Taking the central part of southern margin of Junggar Basin as a case, this study employs geological and geochemical methods to determine the formation mechanism of condensates,waxy and heavy oils in a complicated petroliferous area, and reveals the causes and geochemical processes of the co-occurrence of different types of crude oils in this region. Based on detailed geochemical analyses of more than 40 normal crude oils, light oils,condensates and heavy oils, it is found that the condensates are dominated by low carbon number n-alkanes and enriched in light naphthenics and aromatic hydrocarbons. Heptane values of these condensates range from 19% to 21%, isoheptane values from1.9 to 2.1, and toluene/n-heptane ratios from 1.5 to 2.0. The distribution of n-alkanes in the condensates presents a mirror image with high density waxy crude oils and heavy oils. Combined with the oil and gas-source correlations of the crude oils, condensates and natural gas, it is found that the condensates are product of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils which were derived from mature Cretaceous lacustrine source rocks in the relatively early stage. The waxy oils are the intermediate products of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils, while the heavy oils are in-situ residuals. Therefore, evaporative fractionation and/or phase-controlled fractionation would account for the formation of the condensate, light oil, waxy oil and heavy oil in the central part of southern margin of Junggar Basin, resulting in a great change of the content in terms of light alkanes, naphthenics and aromatics in condensates, followed by great uncertainties of toluene/n-heptane ratios due to migration and re-accumulation. The results suggest that the origin of the condensate cannot be simply concluded by its ratios of toluene/n-heptane and n-heptane/methylcyclohexane on the Thompson's cross-plot, it should be comprehensively determined by the aspects of geological background, thermal history of source rocks and petroleum generation,physical and chemical features of various crude oils and natural gas, vertical and lateral distribution of various crude oils in the study area.

Study of steam heat transfer enhanced by CO_(2) and chemical agents: In heavy oil production

Steam flooding with the assistance of carbon dioxide (CO_(2)) and chemicals is an effective approach for enhancing super heavy oil recovery. However, the promotion and application of CO_(2) and chemical agent-assisted steam flooding technology have been restricted by the current lack of research on the synergistic effect of CO_(2) and chemical agents on enhanced steam flooding heat transfer. The novel experiments on CO_(2)–chemicals cooperate affected steam condensation and seepage were conducted by adding CO_(2) and two chemicals (sodium dodecyl sulfate (SDS) and the betaine temperature-salt resistant foaming agent ZK-05200).According to the experimental findings, a “film” formed on the heat-transfer medium surface following the co-injection of CO_(2) and the chemical to impede the steam heat transfer, reducing the heat transfer efficiency of steam, heat flux and condensation heat transfer coefficient. The steam seepage experiment revealed that the temperature at the back end of the sandpack model was dramatically raised by 3.5–12.8 °C by adding CO_(2) and chemical agents, achieving the goal of driving deep-formation heavy oil. The combined effect of CO_(2) and SDS was the most effective for improving steam heat transfer, the steam heat loss was reduced by 6.2%, the steam condensation cycle was prolonged by 1.3 times, the condensation heat transfer coefficient was decreased by 15.5%, and the heavy oil recovery was enhanced by 9.82%. Theoretical recommendations are offered in this study for improving the CO_(2)–chemical-assisted steam flooding technique.

Petrophysical parameters inversion for heavy oil reservoir based on a laboratory-calibrated frequency-variant rock-physics model

Heavy oil has high density and viscosity, and exhibits viscoelasticity. Gassmann's theory is not suitable for materials saturated with viscoelastic fluids. Directly applying such model leads to unreliable results for seismic inversion of heavy oil reservoir. To describe the viscoelastic behavior of heavy oil, we modeled the elastic properties of heavy oil with varying viscosity and frequency using the Cole-Cole-Maxwell (CCM) model. Then, we used a CCoherent Potential Approximation (CPA) instead of the Gassmann equations to account for the fluid effect, by extending the single-phase fluid condition to two-phase fluid (heavy oil and water) condition, so that partial saturation of heavy oil can be considered. This rock physics model establishes the relationship between the elastic modulus of reservoir rock and viscosity, frequency and saturation. The viscosity of the heavy oil and the elastic moduli and porosity of typical reservoir rock samples were measured in laboratory, which were used for calibration of the rock physics model. The well-calibrated frequency-variant CPA model was applied to the prediction of the P- and S-wave velocities in the seismic frequency range (1–100 Hz) and the inversion of petrophysical parameters for a heavy oil reservoir. The pre-stack inversion results of elastic parameters are improved compared with those results using the CPA model in the sonic logging frequency (∼10 kHz), or conventional rock physics model such as the Xu-Payne model. In addition, the inversion of the porosity of the reservoir was conducted with the simulated annealing method, and the result fits reasonably well with the logging curve and depicts the location of the heavy oil reservoir on the time slice. The application of the laboratory-calibrated CPA model provides better results with the velocity dispersion correction, suggesting the important role of accurate frequency dependent rock physics models in the seismic prediction of heavy oil reservoirs.

Molecular composition of naphthenic acids in a Chinese heavy crude oil and their impacts on oil viscosity

Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the oil viscosity. However, the relationship between the molecular composition of naphthenic acids and oil viscosity is not well understood. This study examined a “clean” heavy oil with low contents of heteroatoms but had a high content of naphthenic acids. Naphthenic acids were fractionated by distillation and caustic extraction. The molecular composition was characterized by high-resolution Orbitrap mass spectrometry. It was found that the 2- and 3-ring naphthenic monoacids with 15–35 carbon atoms are dominant components of the acid fractions;the caustic extraction is capable of isolating naphthenic acids with less than 35 carbons, which is equivalent to the upper limit of the distillable components, but not those in the residue fraction;the total acid number of the heavy distillates is higher than that of the residue fraction;the viscosity of the distillation fraction increases exponentially with an increased boiling point of the distillates. Blending experiments indicates that there is a strong correlation between the oil viscosity and acids content, although the acid content is only a few percent of the total oil.

Thermodynamic study of the removal of heavy metal ions from heavy oils using tetramethyl ammonium hydroxide pentahydrate ionic liquid

This study investigated efficiency of tetramethyl ammonium hydroxide pentahydrate(TMAH)in removal of heavy metal ions from heavy oils obtained from Nigerian oil sands by Soxhlet-extraction technique.Metals were removed from the heavy oils at variable temperatures using TMAH.Elemental analysis was done using Atomic absorption spectrophotometry(AAS).Percentage recovery was≥92.85%,confirming reliability of results.Total metal concentrations followed order:Ni>Pb>Mn>Cu>Cr>Cd.Analysis of variance results showed that F<F_(critical)(0.01<3.68),indicating acceptance of null hypothesis.Cluster analysis result indicated three major inter-elemental clustering groups,indicating chemical affinity and/or similar sources,while T-test result indicated significant differences.Metal removal efficiency decreased with increased temperature,indicating exothermic process.Thermodynamic parameter values were negative,confirming exothermic reactions.Also,negative△DS°values indicated decreased randomness at solid/liquid interface during the extraction.△DG°negative values indicated feasible and spontaneous extraction.Conclusively,the distribution of metals in the analyzed heavy oils followed similar trend,due to similarity in their geological activity,source rock type,maturation and depositional environment.Thermodynamics parameters values showed the extraction process was exothermic,feasible and spontaneous thus,proving metal extraction using TMAH to be efficient.

Effect of operating pressure on the performance of THAI-CAPRI in situ combustion and in situ catalytic process for simultaneous thermal and catalytic upgrading of heavy oils and bitumen

According to the analysis of the 2020 estimates of the International Energy Agency(2020),the world will require up to 770 billion barrels of oil from now to 2040.However,based on the British Petroleum(BP)statistical review of world energy 2020,the world-wide total reserve of the conventional light oil is only 520.2 billion barrels as at the end of 2019.That implies that the remaining 249.8 billion barrels of oil urgently needed to ensure a smooth transition to a decarbonised global energy and economic systems is provided must come from unconventional oils(i.e.heavy oils and bitumen)reserves.But heavy oils and bitumen are very difficult to produce and the current commercial production technologies have poor efficiency and release large quantities of greenhouse gases.Therefore,these resources should ideally be upgraded and produced using technologies that have greener credentials.This is where the energy-efficient,environmentally friendly,and self-sustaining THAI-CAPRI coupled in situ combustion and in situ catalytic upgrading process comes in.However,the novel THAI-CAPRI process is trialled only once at field and it has not gained wide recognition due to poor understanding of the optimal design parameters and procedures.Hence,this work reports the first ever results of investigations of the effect of operating pressure on the performance of the THAI-CAPRI process.Two experimental scale numerical models of the process based on Athabasca tar sand properties were run at pressures of 8000 kPa and 500 kPa respectively using CMG STARS.This study has shown that the higher the operating pressure,the larger the API gravity and the higher the cumulative volume of high-quality oil is produced(i.e.a 2300 cm3 of z24 oAPI oil produced at 8000 kPa versus the 2050 cm3 of z17.5 oAPI oil produced at 500 kPa).The study has further shown that despite presence of annular catalyst layer,the THAI-CAPRI process operates stably.However,it is found that a more stable and safer operation of the process can only be achieved at optimal pressure that should lie between 500 kPa and 8000 kPa,especially since at the lower pressure,should the process time be extended,it will not take long before oxygen breakthrough takes place.The simulations have shown in details that at higher pressures,the catalyst bed is easily and rapidly coked and thus the catalyst life will be very short especially during actual field reservoir operations.Since the oil drainage flux into the HP well at field-scale is different from that at laboratory-scale,and at field-scale,the combustion front does not propagate inside the HP well,it will be practically very challenging to regenerate or replace the coke-deactivated annular catalyst layer in actual reservoir operations.There-fore,it is concluded that during field operation designs,an optimum pressure must be selected such that a balance is obtained between the combustion front stability and the degree of catalytic upgrading,and between the catalyst life and its effectiveness.

Investigation of feasibility of alkali-cosolvent flooding in heavy oil reservoirs

Cold production is a challenge in the case of heavy oil because of its high viscosity and poor fluidity in reservoir conditions.Alkali-cosolvent-polymer flooding is a type of microemulsion flooding with low costs and possible potential for heavy oil reservoirs.However,the addition of polymer may cause problems with injection in the case of highly viscous oil.Hence,in this study the feasibility of alkali-cosolvent(AC)flooding in heavy oil reservoirs was investigated via several groups of experiments.The interfacial tension between various AC formulations and heavy crude oil was measured to select appropriate formulations.Phase behavior tests were performed to determine the most appropriate formulation and conditions for the generation of a microemulsion.Sandpack flooding experiments were carried out to investigate the displacement efficiency of the selected Ac formulation.The results showed that the interfacial tension between an AC formulation and heavy oil could be reduced to below 1o-3 mN/m but differed greatly between different types of cosolvent.A butanol random polyether series displayed good performance in reducing the water-oil interfacial tension,which made it possible to form a Type Il microemulsion in reservoir conditions.According to the results of the phase behavior tests,the optimal salinity for different formulations with four cosolvent concentrations(0.5 wt%,1 wt%,2 wt%,and 3 wt%)was 4000,8000,14000,and 20000 ppm,respectively.The results of rheological measurements showed that Type Ill microemulsion had a viscosity that was ten times that of water.The results of sandpack flooding experiments showed that,in comparison with waterflooding,the injection of a certain Ac formulation slug could reduce the injection pressure.The pressure gradient during waterflooding and AC flooding was around 870 and 30-57 kPa/m,respectively.With the addition of an AC slug,the displacement efficiency was 30%-50%higher than in the case of waterflooding.