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This paper evaluates solvent-based nanofluids for in situ heavy oil upgrading during cyclic steam stimulation (CSS) applications. The study includes a comprehensive analysis of the properties and characteristics of nanofluids, as well as their performance in in situ upgrading and oil recovery. The evaluation includes laboratory experiments to investigate the effects of the nanoparticle's chemical nature, asphaltene adsorption and gasification, heavy oil recovery, and quality upgrading. The results show that alumina-based nanoparticles have a higher efficiency in asphaltene adsorption and catalytic decomposition at low temperatures (<250 °C) than ceria and silica nanoparticles. Specifically, alumina nanoparticles achieved asphaltene adsorption of 48 mg g-1, while ceria adsorbed 42 mg g-1. Alumina and ceria required around 90 and 135 min for 100% asphaltene conversion. Nanofluids were designed by varying nanoparticle and surfactant concentrations dispersed in naphtha, obtaining that the nanofluid containing 0.05 wt % of nanoparticles and 0.05 wt % of surfactant presents the highest yield in increasing API gravity by 5° and reducing oil viscosity by 90% in thermal experiments. Finally, the nanofluid was evaluated under dynamic conditions. The results show that nanofluid-based solvents can significantly improve the recovery and upgrading of heavy oil during CSS applications. When the steam injection technology was assisted by naphtha and nanofluid, 64% and 75% of the original oil in place were recovered, respectively. The effluents obtained in each stage presented lower API gravity values and higher viscosities for those obtained without a nanofluid. Specifically, the API gravity of the recovered oil rose from 11.9° to 34°, and the viscosity decreased to below 100 cP. The paper concludes by highlighting the potential of nanofluid-based solvents as a promising technology for heavy oil recovery and upgrading in the future.
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The use of carriers to improve cannabidiol (CBD) bioavailability during digestion is at the forefront of research. The main objective of this research was to evaluate CBD bioactivity and develop CBD composites based on tailored carbon support to improve availability under digestive conditions. The antioxidant capacity of CBD was evaluated using spectrophotometric methods, and anti-proliferative assays were carried out using human colon carcinoma cells (SW480). Twenty-four composites of CBD + carbon supports were developed, and CBD desorption tests were carried out under simulated digestive conditions. The antioxidant capacity of CBD was comparable to and superior to Butylhydrox-ytoluene (BHT), a commercial antioxidant. CBD reflected an IC-50 of 10,000 mg/L against SW480 cancer cells. CBD in biological systems can increase the shelf life of lipid and protein foods by 7 and 470 days, respectively. Finally, acid carbons showed major CBD adsorption related to electrostatic interactions, but basic carbons showed better delivery properties related to electrostatic repulsion. A tailored composite was achieved with a CBD load of 27 mg/g with the capacity to deliver 1.1 mg, 21.8 mg, and 4 mg to the mouth, stomach, and duodenum during 18 h, respectively. This is a pioneering study since the carriers were intelligently developed to improve CBD release.
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This study aimed to develop and implement a nanotechnology-based alternative to traditional tracers used in the oil and gas industry for assessing interwell connectivity. A simple and rapid hydrothermal protocol for synthesizing carbon quantum dots (CQDs) using agroindustry waste was implemented. Three commercial CQDs were employed (CQDblue, CQDgreen, and CQDred); the fourth was synthesized from orange peel (CQDop). The CQDs from waste and other commercials with spherical morphology, nanometric sizes less than 11 nm in diameter, and surface roughness less than 3.1 nm were used. These tracers demonstrated high colloidal stability with a negative zeta potential, containing carbonyl-type chemical groups and unsaturations in aromatic structures that influenced their optical behavior. All materials presented high colloidal stability with negative values of charge z potential between -17.8 and -49.1. Additionally, individual quantification of these tracers is feasible even in scenarios where multiple CQDs are present in the effluent with a maximum percentage of interference of 15.5% for CQDop in the presence of the other three nanotracers. The CQDs were injected into the field once the technology was insured under laboratory conditions. Monitoring the effluents allowed the determination of connectivity for five first-line producer wells. This study enables the application of CQDs in the industry, particularly in fields where the arrangement of injector and producer wells is intricate, requiring the use of multiple tracers for a comprehensive description of the system.
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Microfluidic models have become essential instruments for studying enhanced oil recovery techniques through fluid and chemical injection into micromodels to observe interactions with pore structures and resident fluids. The widespread use of cost-effective lab-on-a-chip devices, known for efficient data extraction and minimal reagent usage, has driven demand for efficient data management methods crucial for high-performance data and image analyses. This article introduces a semiautomatic method for calculating oil recovery in polymeric nanofluid flooding experiments based on the background subtraction (BSEO). It employs the background subtraction technique, generating a foreground binary mask to detect injected fluids represented as pixel areas. The pixel difference is then compared to a threshold value to determine whether the given pixel is foreground or background. Moreover, the proposed method compares its performance with two other representative methods: the ground truth (manual segmentation) and Fiji-ImageJ software. The experiments yielded promising results. Low values of mean-squared error (MSE), mean absolute error (MAE), and root-mean-squared error (RMSE) indicate minimal prediction errors, while a substantial coefficient of determination (R2) of 98% highlights the strong correlation between the method's predictions and the observed outcomes. In conclusion, the presented method emphasizes the viability of BSEO as a robust alternative, offering the advantages of reduced computational resource usage and faster processing times.
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Scleroglucan (SG) is resistant to harsh reservoir conditions such as high temperature, high shear stresses, and the presence of chemical substances. However, it is susceptible to biological degradation because bacteria use SG as a source of energy and carbon. All degradation effects lead to viscosity loss of the SG solutions, affecting their performance as an enhanced oil recovery (EOR) polymer. Recent studies have shown that nanoparticles (NPs) can mitigate these degradative effects. For this reason, the EOR performance of two new nanohybrids (NH-A and NH-B) based on carboxymethyl-scleroglucan and amino-functionalized silica nanoparticles was studied. The susceptibility of these products to chemical, mechanical, and thermal degradation was evaluated following standard procedures (API RP 63), and the microbial degradation was assessed under reservoir-relevant conditions (1311 ppm and 100 °C) using a bottle test system. The results showed that the chemical reactions for the nanohybrids obtained modified the SG triple helix configuration, impacting its viscosifying power. However, the nanohybrid solutions retained their viscosity during thermal, mechanical, and chemical degradation experiments due to the formation of a tridimensional network between the nanoparticles (NPs) and the SG. Also, NH-A and NH-B solutions exhibited bacterial control because of steric hindrances caused by nanoparticle modifications to SG. This prevents extracellular glucanases from recognizing the site of catalysis, limiting free glucose availability and generating cell death due to substrate depletion. This study provides insights into the performance of these nanohybrids and promotes their application in reservoirs with harsh conditions.
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In this study, two new nanohybrids (NH-A and NH-B) were synthesized through carbodiimide-assisted coupling. The reaction was performed between carboxymethyl-scleroglucans (CMS-A and CMS-B) with different degrees of substitution and commercial amino-functionalized silica nanoparticles using 4-(dimethylamino)-pyridine (DMAP) and N,N'-dicyclohexylcarbodiimide (DCC) as catalysts. The morphology and properties of the nanohybrids were investigated by using transmission (TEM) and scanning electron microscopy (SEM), electron-dispersive scanning (EDS), attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FT-IR), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic light scattering (DLS). The nanohybrids exhibited differences in structure due to the incorporation of polyhedral oligomeric silsesquioxane (POSS) materials. The results reveal that hybrid nanomaterials exhibit similar thermal properties but differ in morphology, chemical structure, and crystallinity properties. Finally, a viscosity study was performed on the newly obtained nanohybrid materials; viscosities of nanohybrids increased significantly in comparison to the carboxymethyl-scleroglucans, with a viscosity difference of 7.2% for NH-A and up to 32.6% for NH-B.
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Among the Enhanced Oil Recovery (EOR) methods, gas-based EOR methods are very popular all over the world. The gas injection has a high ability to increase microscopic sweep efficiency and can increase production efficiency well. However, it should be noted that in addition to all the advantages of these methods, they have disadvantages such as damage due to asphaltene deposition, unfavorable mobility ratio, and reduced efficiency of macroscopic displacement. In this paper, the gas injection process and its challenges were investigated. Then the overcoming methods of these challenges were investigated. To inhibit asphaltene deposition during gas injection, the use of nanoparticles was proposed, which were examined in two categories: liquid-soluble and gas-soluble, and the limitations of each were examined. Various methods were used to overcome the problem of unfavorable mobility ratio and their advantages and disadvantages were discussed. Gas-phase modification has the potential to reduce the challenges and limitations of direct gas injection and significantly increase recovery efficiency. In the first part, the introduction of gas injection and the enhanced oil recovery mechanisms during gas injection were mentioned. In the next part, the challenges of gas injection, which included unfavorable mobility ratio and asphaltene deposition, were investigated. In the third step, gas-phase mobility control methods investigate, emphasizing thickeners, thickening mechanisms, and field applications of mobility control methods. In the last part, to investigate the effect of nanoparticles on asphaltene deposition and reducing the minimum miscible pressure in two main subsets: 1- use of nanoparticles indirectly to prevent asphaltene deposition and reduce surface tension and 2- use of nanoparticles as a direct asphaltene inhibitor and Reduce MMP of the gas phase in crude oil was investigated.
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Biopolymers emerge as promising candidates for enhanced oil recovery (EOR) applications due to their molecular structures, which exhibit better stability than polyacrylamides under harsh conditions. Nonetheless, biopolymers are susceptible to oxidation and biological degradation. Biopolymers reinforced with nanoparticles could be a potential solution to the issue. The nanofluids' stability and performance depend on the nanoparticles' properties and the preparation method. The primary objective of this study was to evaluate the effect of the preparation method and the nanoparticle type (SiO2, Al2O3, and TiO2) on the viscosity and stability of the scleroglucan (SG). The thickening effect of the SG solution was improved by adding all NPs due to the formation of three-dimensional structures between the NPs and the SG chains. The stability test showed that the SG + Al2O3 and SG + TiO2 nanofluids are highly unstable, but the SG + SiO2 nanofluids are highly stable (regardless of the preparation method). According to the ANOVA results, the preparation method and standing time influence the nanofluid viscosity with a statistical significance of 95%. On the contrary, the heating temperature and NP type are insignificant. Finally, the nanofluid with the best performance was 1000 ppm of SG + 100 ppm of SiO2_120 NPs prepared by method II.
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This paper presents the methodology for synthesizing and characterizing two carboxymethyl EOR-grade Scleroglucans (CMS-A and CMS-B). An O-Alkylation reaction was used to insert a hydrophilic group (monochloroacetic acid-MCAA) into the biopolymer's anhydroglucose subunits (AGUs). The effect of the degree of the carboxymethyl substitution on the rheology and thermal stability of the Scleroglucan (SG) was also evaluated. Simultaneous thermal analysis (STA/TGA-DSC), differential scanning calorimetry (DSC), X-ray Diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Scanning Electron Microscopy, and Energy Dispersive Spectroscopy (SEM/EDS) were employed to characterize both CMS products. FTIR analysis revealed characteristic peaks corresponding to the carboxymethyl functional groups, confirming the modification. Also, SEM analysis provided insights into the structural changes in the polysaccharide after the O-Alkylation reaction. TGA results showed that the carboxymethylation of SG lowered its dehydroxylation temperature but increased its thermal stability above 300 °C. The CMS products and SG exhibited a pseudoplastic behavior; however, lower shear viscosities and relaxation times were observed for the CMS products due to the breakage of the SG triple helix for the chemical modification. Despite the viscosity results, the modified Scleroglucans are promising candidates for developing new engineering materials for EOR processes.
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Cannabidiol (CBD) has significant therapeutic potential; nevertheless, its advance as an effective drug by the pharmaceutical business is hindered by its inherent characteristics, such as low bioavailability, low water solubility, and variable pharmacokinetic profiles. This research aimed to develop nanoliposomes using an easy and low-cost method to improve the hydrosolubility of CBD and achieve a controlled delivery of the active principle under relevant physiological conditions from the mouth to the intestine; the cytotoxic and antitumor activities were also evaluated. To achieve the objective, core-shell nanoliposomes based on CBD were synthesized in three easy steps and characterized in terms of shape, size, surface chemistry, thermal capacity, and surface charge density through transmission electron microscopy (TEM), dynamic light scattering (DLS), Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and potential charge (PZ), respectively. CBD-controlled delivery trials were carried out under simulated mouth-duodenal conditions and fitted to Korsmeyer-Peppas and Noyes-Whitney models to conclude about the pharmacokinetics of CBD from nano-CBD. Cytotoxicity studies on nonmalignant human keratinocytes (HaCaT) were carried out to evaluate its safety and the recommended consumption dose, and finally, the antiproliferative capacity of nano-CBD on human colon carcinoma cells (SW480) was determined as beginning proposal for cancer treatment. The characterization results verified the water solubility for the CBD nanoencapsulated, the core-shell structure, the size in the nanometric regime, and the presence of the synthesis components. The dissolution rate at duodenal conditions was higher than that in buccal and stomach environments, respectively, and this behavior was associated with the shell (lecithin) chemical structure, which destabilizes at pH above 7.2, allowing the release by non-Fickian diffusion of CBD as corroborated by the Korsmeyer-Peppas model. In vitro biological tests revealed the innocuousness and cyto-security of nano-CBD up to 1000 mg·L-1 when evaluated on HaCaT cells and concentrations higher than 1000 mg·L-1 showed antitumor activity against human colon carcinoma cells (SW480) taking the first step as a chemotherapeutic proposal. These results are unprecedented and propose a selective delivery system based on nano-CBD at low cost and that provides a new form of administration and chemo treatment.
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Wax deposition in high-wax (waxy) crude oil has been an important challenge in the oil and gas industry due to the repercussions in flow assurance during oil extraction and transportation. However, the nanotechnology has emerged as a potential solution for the optimization of conventional wax removal and/or inhibition processes due to its exceptional performance in the alteration of wax morphology and co-crystallization behavior. In this sense, this study aims to study the performance of two commercial wax inhibitor treatments (WT1 and WT2) on the wax formation and crystallization due to the addition of SiO2 nanoparticles. Differential scanning calorimetry experiments and cold finger tests were carried out to study the effect of the WT on wax appearance temperature (WAT) and the wax inhibition efficiency (WIE) in a scenario with an initial temperature difference. In the first stage, the behavior of both WT in the inhibition of wax deposition was achieved, ranging in the concentration of the WT in the waxy crude (WC) oil from 5000 to 50,000 mg·L-1. Then, NanoWT was prepared by the addition of SiO2 nanoparticles on WT1 and WT2 for concentrations between 1000 and 500 mg·L-1, and the performance of the prepared NanoWT was studied at the best concentration of WIT in the absence of nanoparticles. Finally, the role of the nanofluid concentration in wax inhibition was accomplished for the best NanoWT. Selected NanoWT with nanoparticle dosage of 100 mg·L-1 added to WC oil at 5000 mg·L-1 displays reductions in WAT and WIE of 15.3 and 71.6 for NanoWT1 and -2.2 and 42.5% for NanoWT2. In flow loop experiments for the crude oil at temperatures above (30 °C) and below (16 °C), the WAT value indicates an increase of 8.3 times the pressure drops when the crude oil is flowing at a temperature below the WAT value. Therefore, when NanoWT1 is added to the crude oil, a reduction of 31.8% was found in the pressure drop in comparison with the scenario below the WAT value, ensuring the flow assurance in the pipeline in an unfavorable environment. Based on the pressure-drop method, a reduction greater than 5% in the wax deposit thickness confirms the wax deposition inhibitory character of the designed NanoWT.
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The objective of this study is to evaluate the role of nanoparticles with different chemical structures in completion fluids (CF) in providing a positive dual effect for well stimulation and clay swelling damage inhibition. Six types of commercial (C) or synthesized (S) nanoparticles have been incorporated into a commercial completion fluid. Doses varied between 100 and 500 mg·L-1. CF-nanoparticles were evaluated by fluid-fluid, fluid-nanoparticle, and fluid-rock interactions. The adsorption isotherms show different degrees of affinity, which impacts on the reduction of the interfacial tension between the CF and the reservoir fluids. Fluid-fluid interactions based on interfacial tension (IFT) measurements suggest that positively charged nanoparticles exhibit high IFT reductions. Based on contact angle measurements, fluid-rock interactions suggest that ZnO-S, SiO2-C, SiO2-S, and ZrO2 can adequately promote water-wet rock surfaces compared with other nanomaterials. According to the capillary number, ZnO-S and MgO-S have a higher capacity to reduce both interfacial and surface restrictions for crude oil production, suggesting that completion fluid with nanoparticles (NanoCF) can function as a stimulation agent. The clay swelling inhibition test in the presence of ZnO-S-CTAB and MgO-S-CTAB nanoparticles showed a 28.6% decrease in plastic viscosity (PV), indicating a reduction in clay swelling. The results indicate that a high-clay environment can meet the completion fluid's requirements. They also indicate that the degree of clay swelling inhibition of the nanoparticles depends on their chemical nature and dosage. Finally, displacement tests revealed that CF with nanoparticles increased the oil linear displacement efficiency.
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The increase in the global demand for energy and fossil fuel dependency is hindering efforts to reduce greenhouse gas (GHG) emissions. Geothermal resources supplement this increase in energy demand with reduced emissions because of their availability, base-load production profile, and climatic independence. Despite these advantages, the development of geothermal energy is limited because of different reasons such as subsurface exploration risk and high upfront capital cost for drilling and facility construction. However, similarities in infrastructure and operations between the oil and gas industry and the geothermal industry can optimize expense and development when exploiting geothermal resources. Thus, in this review, we present recent advances and applications of geothermal power systems in the oil and gas industry starting from the fundamentals and basic principles of geothermal energy and the organic Rankine cycle (ORC). These applications include the use of geothermal resources via abandoned wells, active wells, and paired thermal enhanced oil recovery processes with injection for fluid heating and energy production. Abandoned wells are alternatives that reduce costs in geothermal energy-use projects. The use of geothermal resources via active wells allows the valorization of a resource, such as the production of water, which is considered a byproduct of production activities in an oilfield. The use of thermally enhanced oil recovery processes enhances the energy conditions of fluids produced in the field, improving geothermal systems with fluids at higher temperatures. Finally, an overview is presented of the challenges and opportunities of geothermal energy in the oil industry where the requirement to improve the usage of technologies, such as the ORCs, with the working fluids used in the cycles, is highlighted. Furthermore, the importance of environmental studies and use of novel tools, such as nanotechnology, to improve the efficiency of geothermal energy usage is highlighted.
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This study aimed to develop novel bio-nanofluids using Solanum torvum extracts in synergy with nanoparticles of different chemical nature as a proposal sustainable for enhanced oil recovery (EOR) applications. For this, saponin-rich extracts (SRE) were obtained from Solanum torvum fruit using ultrasound-assisted and Soxhlet extraction. The results revealed that Soxhlet is more efficient for obtaining SRE from Solanum torvum and that degreasing does not generate additional yields. SRE was characterized by Fourier transformed infrared spectrophotometry, thermogravimetric analysis, hydrophilic-lipophilic balance, and critical micelle concentration analyses. Bio-nanofluids based on SiO2 (strong acid), ZrO2 (acid), Al2O3 (neutral), and MgO (basic) nanoparticles and SRE were designed to evaluate the effect of the chemical nature of the nanoparticles on the SRE performance. The results show that 100 mg L-1 MgO nanoparticles improved the interfacial tension up to 57% and the capillary number increased by two orders of magnitude using this bio-nanofluid. SRE solutions enhanced with MgO recovered about 21% more than the system in the absence of nanoparticles. The addition of MgO nanoparticles did not cause a loss of injectivity. This is the first study on the surface-active properties of Solanum torvum enhanced with nanomaterials as an environmentally friendly EOR process.
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Pollution by dyes and heavy metals is one of the main concerns at the environmental level due to their toxicity and inefficient elimination by traditional water treatment. Orange peel (OP) without any treatment was applied to effectively eliminate methylene blue (MB) and cadmium ions (Cd2+) in mono- and multicomponent systems. Although the single adsorption processes for MB and Cd2+ have been investigated, the effects and mechanisms of interactions among multicomponent systems are still unclear. Batch experiments showed that in monocomponent systems, the maximum adsorption capacities were 0.7824 mmol g-1 for MB and 0.2884 mmol g-1 for Cd2+, while in multicomponent systems (Cd2+ and MB), both contaminants competed for the adsorption sites on OP. Particularly, a synergic effect was observed since the adsorption capacity of Cd2+ increased compared to the monocomponent system. Results of desorption and adsorbent reuse confirmed that the adsorbent presents good regeneration performance. The low cost of this material and its capacity for the individual or simultaneous removal of Cd2+ and MB in aqueous solutions makes it a potential adsorbent for polluted water treatment processes.
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Citrus sinensis , Poluentes Químicos da Água , Purificação da Água , Adsorção , Cádmio , Concentração de Íons de Hidrogênio , Cinética , Azul de Metileno , Águas Residuárias , Purificação da Água/métodosRESUMO
This study aims to develop and evaluate fracturing nanofluids from the laboratory to the field trial with the dual purpose of increasing heavy crude oil mobility and reducing formation damage caused by the remaining fracturing fluid (FF). Two fumed silica nanoparticles of different sizes, and alumina nanoparticles were modified on the surface through basic and acidic treatments. The nanoparticles were characterized by transmission electron microscopy, dynamic light scattering, zeta potential and total acidity. The rheological behavior of the linear gel and the heavy crude oil after adding different chemical nature nanoparticles were measured at two concentrations of 100 and 1000 mg/L. Also, the contact angle assessed the alteration of the rock wettability. The nanoparticle with better performance was the raw fumed silica of 7 nm at 1000 mg/L. These were employed to prepare a fracturing nanofluid from a commercial FF. Both fluids were evaluated through their rheological behavior as a function of time at high pressure following the API RP39 test, and spontaneous imbibition tests were carried out to assess the FF's capacity to modify the wettability of the porous media. It was possible to conclude that the inclusion of 7 nm commercial silica nanoparticles allowed obtaining a reduction of 10 and 20% in the two breakers used in the commercial fracture fluid formulation without altering the rheological properties of the system. Displacement tests were also performed on proppant and rock samples at reservoir conditions of overburden and pore pressures of 3200 and 1200 psi, respectively, while the temperature was set at 77 °C and the flow rate at 0.3 cm3/min. According to the effective oil permeability, a decrease of 31% in the damage was obtained. Based on these results, the fracturing nanofluid was selected and used in the first worldwide field application in a Colombian oil field with a basic sediment and water (BSW%) of 100 and without oil production. After two weeks of the hydraulic fracture operation, crude oil was produced. Finally, one year after this work, crude oil viscosity and BSW% kept showing reductions near 75% and 33%, respectively; and having passed two years, the cumulative incremental oil production is around 120,000 barrels.
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This study focuses on evaluating the volumetric hydrogen content in the gaseous mixture released from the steam catalytic gasification of n-C7 asphaltenes and resins II at low temperatures (<230 °C). For this purpose, four nanocatalysts were selected: CeO2, CeO2 functionalized with Ni-Pd, Fe-Pd, and Co-Pd. The catalytic capacity was measured by non-isothermal (from 100 to 600 °C) and isothermal (220 °C) thermogravimetric analyses. The samples show the main decomposition peak between 200 and 230 °C for bi-elemental nanocatalysts and 300 °C for the CeO2 support, leading to reductions up to 50% in comparison with the samples in the absence of nanoparticles. At 220 °C, the conversion of both fractions increases in the order CeO2 < Fe-Pd < Co-Pd < Ni-Pd. Hydrogen release was quantified for the isothermal tests. The hydrogen production agrees with each material's catalytic activity for decomposing both fractions at the evaluated conditions. CeNi1Pd1 showed the highest performance among the other three samples and led to the highest hydrogen production in the effluent gas with values of ~44 vol%. When the samples were heated at higher temperatures (i.e., 230 °C), H2 production increased up to 55 vol% during catalyzed n-C7 asphaltene and resin conversion, indicating an increase of up to 70% in comparison with the non-catalyzed systems at the same temperature conditions.
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Manganese ferrite solid nanospheres (MSNs) were prepared by a solvothermal method and calcined at various temperatures up to 500 °C. Their surface area, morphology, particle size, weight change during calcination, surface coordination number of metal ions, oxidation state, crystal structure, crystallite size, and magnetic properties were studied. The MSNs were used as catalysts to activate potassium peroxymonosulfate (PMS) for the oxidative degradation of para-nitrophenol (PNP) from water and for the oxidation of n-C7 asphaltenes in flowing air at atmospheric (0.084 MPa) and high pressure (6 MPa). Mn was in oxidation states (II) and (III) at calcination temperature of 200 °C, and the crystalline structure corresponded to jacobsite. Mn was in oxidation states (III) and (IV) at 350 °C and in oxidation states (II), (III), and (IV) at 500 °C, and the crystalline structure was maghemite at both temperatures. MSN catalysts generated hydroxyl (HO·) and sulfate (SO4·-) radicals in the PMS activation and generated HO· radicals in the n-C7 asphaltene oxidation. In both reactions, the best catalyst was MSN calcined at 350 °C (MSN350), because it has the highest concentration of Mn(III) in octahedral B sites, which are directly exposed to the catalyst surface, and the largest total and lattice oxygen contents, favoring oxygen mobility for Mn redox cycles. The MSN350 sample reduces the decomposition temperature of n-C7 asphaltenes from 430 to 210 °C at 0.084 MPa and from 370 to 200 °C at 6.0 MPa. In addition, it reduces the effective activation energy by approximately 77.6% in the second combustion (SC) region, where high-temperature oxidation reactions take place.
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Nanosferas , Catálise , Nitrofenóis , Oxirredução , Peróxidos , Hidrocarbonetos Policíclicos AromáticosRESUMO
This study aims to evaluate the behavior of Cardanol/SiO2 nanocomposites in the inhibition of the asphaltene damage based on the coreflooding test at reservoir conditions. The nanocomposite design was performed in Part I (https://doi.org/10.1021/acs.energyfuels.0c01114), leading to SiO2 nanoparticles functionalized with different mass fractions of cardanol on the surface of 5 (5CSN), 7 (7CSN), and 9% (9CSN). In this part of the study, the nanocomposite/reservoir fluid interactions were evaluated through interfacial tension measurements and nanocomposite/rock surface interactions using water imbibition and contact angle measurements. Results showed that the designed nanocomposite leads to a reduction of interfacial tension of 82.6, 61.7, and 51.4% for 5CSN, 7CSN, and 9CSN regarding silica support (SN). Whereas, the reduction of the Si-OH functional groups from SiO2 nanoparticles due to the increase of the cardanol content affects the effectiveness of the wettability alteration for 7CSN and 9CSN. Nevertheless, when 5CSN is evaluated, the system is altered from an oil-wet to a mixed-wet state. Coreflooding tests at reservoir conditions were performed to evaluate the oil recovery after asphaltene damage, after damage removal and nanofluid injection, and after induction of a second asphaltene damage to check inhibition. Results show that the selected nanocomposites at a dosage of 300 mg·L-1 enhance the oil recovery in comparison with the baseline conditions via the reduction of the interfacial/surface forces at the pore scale and wettability alteration. It is worth to remark that this improvement remains after the second asphaltene damage induction, which proves the high inhibitory capacity of the designed nanocomposite for the asphaltene precipitation/deposition. Also, the use of the nanocomposites favors the oil recovery more than 50% compared to the asphaltene damage scenario.
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The primary objective of this study is to develop a novel experimental nanofluid based on surfactant-nanoparticle-brine tuning, subsequently evaluate its performance in the laboratory under reservoir conditions, then upscale the design for a field trial of the nanotechnology-enhanced surfactant injection process. Two different mixtures of commercial anionic surfactants (SA and SB) were characterized by their critical micelle concentration (CMC), density, and Fourier transform infrared (FTIR) spectra. Two types of commercial nanoparticles (CNA and CNB) were utilized, and they were characterized by SBET, FTIR spectra, hydrodynamic mean sizes (dp50), isoelectric points (pHIEP), and functional groups. The evaluation of both surfactant-nanoparticle systems demonstrated that the best performance was obtained with a total dissolved solid (TDS) of 0.75% with the SA surfactant and the CNA nanoparticles. A nanofluid formulation with 100 mg·L-1 of CNA provided suitable interfacial tension (IFT) values between 0.18 and 0.15 mN·m-1 for a surfactant dosage range of 750-1000 mg·L-1. Results obtained from adsorption tests indicated that the surfactant adsorption on the rock would be reduced by at least 40% under static and dynamic conditions due to nanoparticle addition. Moreover, during core flooding tests, it was observed that the recovery factor was increased by 22% for the nanofluid usage in contrast with a 17% increase with only the use of the surfactant. These results are related to the estimated capillary number of 3 × 10-5, 3 × 10-4, and 5 × 10-4 for the brine, the surfactant, and the nanofluid, respectively, as well as to the reduction in the surfactant adsorption on the rock which enhances the efficiency of the process. The field trial application was performed with the same nanofluid formulation in the two different injection patterns of a Colombian oil field and represented the first application worldwide of nanoparticles/nanofluids in enhanced oil recovery (EOR) processes. The cumulative incremental oil production was nearly 30,035 Bbls for both injection patterns by May 19, 2020. The decline rate was estimated through an exponential model to be -0.104 month-1 before the intervention, to -0.016 month-1 after the nanofluid injection. The pilot was designed based on a production increment of 3.5%, which was successfully surpassed with this field test with an increment of 27.3%. This application is the first, worldwide, to demonstrate surfactant flooding assisted by nanotechnology in a chemical enhanced oil recovery (CEOR) process in a low interfacial tension region.