Oil Upgrading Research Articles

Optimizing in-situ upgrading of heavy crude oil via catalytic aquathermolysis using a novel graphene oxide-copper zinc ferrite nanocomposite as a catalyst

Unconventional resources, such as heavy oil, are increasingly being explored and exploited due to the declining availability of conventional petroleum resources. Heavy crude oil poses challenges in production, transportation, and refining, due to its high viscosity, low API gravity, and elevated sulfur and metal content. Improving the quality of heavy oil can be achieved through the application of steam injection, which lowers the oil’s viscosity and enhances its flow. However, steam injection alone falls short of meeting the growing demand for higher-quality petroleum products. Catalytic upgrading is therefore being investigated as a viable solution to improve heavy oil quality. This study experimentally investigates the application of two novel catalysts, namely copper-substituted zinc ferrite (ZCFO) synthesized via the sol–gel combustion method and a graphene oxide-based nanocomposite (GO-ZCFO) with different ratios, for catalyzing aquathermolysis reactions in the steam injection process, with the aim of enhancing the in-situ upgrading of heavy oil. These catalysts underwent characterization using X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Transmission Electron Microscopy (TEM). Their catalytic performance was assessed utilizing a high-pressure/high-temperature reactor (300 ml), with a comprehensive analysis of the changes in the physical and chemical properties of the heavy oil before and after upgrading. This analysis included measurements of sulfur content, SARA fractions, viscosity, API gravity, and Gas Chromatography (GC) of saturated hydrocarbons and evolved gases. All upgrading experiments, including both catalytic and non-catalytic aquathermolysis processes, were conducted under a reaction time of 6 h, a reaction temperature of 320 °C, and high pressure (86–112 bar). The results indicated that the introduction of the proposed catalysts as additives into the upgrading system resulted in a significant reduction in sulfur content. This, in turn, led to a decrease in resin and asphaltene content, an increase in the content of saturated hydrocarbon, particularly low-molecular-weight alkanes, and ultimately, a reduction in viscosity along with higher API gravity of the crude oil. GO-ZCFO with a weight ratio (50:50) exhibited the best catalytic performance. The heavy crude oil, upgraded with this 50:50 ratio, exhibited significant enhancements, including a 29.26% reduction in sulfur content, a 21.27% decrease in resin content, a 37.60% decrease in asphaltene content, a 46.92% increase in saturated hydrocarbon content, a 66.48% reduction in viscosity, and a 25.49% increase in API gravity. In comparison, the oil upgraded through non-catalytic aquathermolysis showed only marginal improvements, with slight reductions in sulfur content by 5.41%, resin content by 3.60%, asphaltene content by 11.36%, viscosity by 17.89%, and inconsiderable increases in saturated hydrocarbon content by 9.9% and API gravity by 3.02%. The GO-ZCFO, with its high catalytic activity, stands as a promising catalyst that contributes to improving the in-situ upgrading and thermal conversion of heavy crude oil.

Selective catalytic conversion of model olefin and diolefin compounds of waste plastic pyrolysis oil: Insights for light olefin production and coke minimization

The primary challenges in ex-situ catalytic pyrolysis of plastic waste to produce light olefins lie in the selective conversion of larger olefins and diolefins downstream of the pyrolyzer. Hence, the catalytic cracking mechanism of plastic pyrolysis oil was explored using an α-olefin (1-decene) and a diolefin (1,9-decadiene) model compounds over an HZSM-5 zeolite-based catalyst in a fixed-bed reactor. Key objectives were to elucidate the reaction pathways for light olefin production, aromatization, and coke formation in catalytic cracking of larger olefins and diolefins. The investigation explored the impact of HZSM-5 steam treatment severity, contact time (∼58–226 ms), and reaction temperature (250–450 °C) on product yields. The severity of steam treatment was found to increase the 1-decene isomerization rate while decreasing the cracking rate and conversion of 1-decene to C3-4 light olefins. In the catalytic cracking of 1-decene, major product types included olefins (linear and nonlinear) and a few naphthenes, while in the case of 1,9-decadiene catalytic cracking, non-linear olefins were absent, with abundant naphthenes followed by lighter diolefins and C3-5 linear olefins. Temperature and contact time variations revealed that the catalytic cracking of 1-decene initiated with double bond rearrangement isomerization, progressing to skeletal isomerization, and intensified cracking reactions producing light C3-4 olefins. Conversely, in the catalytic cracking of 1,9-decadiene, cyclization was the primary reaction pathway, followed by β-scission, resulting in lighter conjugated dienes and light linear olefins. Thermal gravimetric analysis (TGA) of spent catalysts confirmed a higher coke amount generated during 1,9-decadiene cracking compared to 1-decene cracking, indicating that diene compounds serve as precursors for significant coke formation in plastic pyrolysis oil. These insights provide valuable understanding for catalytic upgrading of pyrolysis oil from polyolefin pyrolysis.

Combustion behavior and effluent liquid properties in extra-heavy crude oil reservoirs developed by steam huff and puff

In recent years, interest in in-situ combustion (ISC) as an alternative technique for extra-heavy crude oil reservoirs subjected to steam huff and puff has grown significantly; however, the ISC behavior and effluent liquid properties in such oil reservoirs remain under-explored. In this work, the combustion tube (CT) was used to investigate the combustion behavior of extra-heavy crude oil. Also, the effluent liquid properties during ISC were analyzed comprehensively. The results revealed that when the secondary water bodies (SWB) were present at the injection end of CT, a stable combustion front advanced, causing a gradual temperature rise and a CO2 concentration above 12 % in the effluent gas. This suggested that steam injection wells in these reservoirs were suitable candidates for subsequent air injection after steam huff and puff. Conversely, when the SWB was located at the production end of CT, the peak temperature of combustion decreased, indicating a transition to medium-temperature combustion and unstable combustion front advancement, making steam injection wells unsuitable for ISC as production ones. Three key criteria for evaluating ISC effectiveness in extra-heavy crude oil were: (1) the intensity of –CH2 and –CH3 peaks, (2) the C-O absorption peak between 1100 and 1000 cm−1, and (3) the distribution of characteristic peaks around 750 cm−1. A significant decrease in these peaks indicated high-temperature combustion and substantial oil upgrading. Also, the presence of alkynes suggested extensive thermal cracking and a stable combustion front. The anion concentration of effluent water increased compared to crude water, but the relationship between water ion concentration and combustion state was weak, without a discernible pattern.

Conversion of kraft lignin to hydrocarbons using an integrated molten salt pyrolysis/catalytic hydrotreatment approach

Thermochemical conversion of underutilized lignocellulosic streams such as kraft lignin from the pulp and paper industry has the potential to produce sustainable chemicals and biofuels. We here report a process to continuously convert softwood-based lignoboost lignin to hydrocarbons using a three-step approach: i) liquefaction/dispersion of the lignin in a suitable molten salt, ii) pyrolysis of the liquefied/dispersed lignin in a molten salt mixture (ZnCl2, KCl, and NaCl), to obtain a crude lignin oil and iii) upgrading of the lignin oil using a catalytic hydrotreatment to yield hydrocarbons. Step 1 and 2 were integrated using a twin screw extruder with different heating sections at a scale of 20 g/h lignin input. Besides char, a lignin oil, mainly composed of monomeric phenolics, and propylene were the major products. The highest yield of the latter two products was around 32 wt% (23 wt% crude lignin oil and 9 wt% propylene). The lignin oil was subsequently converted to hydrocarbons using a two-step catalytic hydrotreatment approach (stabilization step using CoMo/Al2O3 catalyst and a further deep hydrotreatment over a NiMo/Al2O3 catalyst). The final liquid product contained less than 0.5 wt% of oxygen and was shown to be rich in (cyclo)alkanes and aromatic hydrocarbons. The carbon yield for the overall conversion of lignin to hydrocarbons was 23 %.

Hydrothermal liquefaction of southern yellow pine with downstream processing for improved fuel grade chemicals production

The hydrothermal liquefaction (HTL) technique for liquefying lignocellulose biomass feedstock is often associated with low biocrude yield and poor fuel properties. This study examined the HTL of southern yellow pine sawdust and the hydrotreatment (HYD) of produced biocrudes in an effort to address these challenges. Pine HTL treatment was performed within water and water–ethanol mixed reaction medium at 250, 300, and 350℃ temperatures using metallic iron (Fe) as a catalyst. The rising reaction temperature in a water medium and increasing ethanol content in a mixed reaction medium were found to be effective in enhancing the biocrude yield from the non-catalytic pine HTL process. Maximum non-catalytic biocrude yield of 18 wt.% was produced in water at 350℃, whereas the ethanol and water (1:1 on mass basis) mixture generated the highest biocrude yield of 34 wt.% at 300℃ without any catalyst. The iron catalyst facilitated a maximum of 29 wt.% of biocrude yield as opposed to 18 wt.% without the catalyst at 350℃ in water. The use of an iron catalyst also raised the calorific value of produced biocrudes by 2.5–14 % within 250-350℃ in both water and water–ethanol media. The catalytic and non-catalytic biocrude products were chosen to undergo HYD treatment at 400 °C under high hydrogen pressure (initial 1000 psi) using an alumina-supported cobalt-molybdenum catalyst. The HYD treatment reduced the oxygen content of upgraded oils by 36–60 % compared to the parent HTL biocrudes with 35–37 MJ/kg calorific values. The simulated distillation detected the maximum gasoline range compounds in upgraded oil from catalyst and water–ethanol conditions, whereas the GC–MS analysis revealed the production of increased aromatic hydrocarbons in all upgraded HYD oils. This work has demonstrated the potential of ethanol and inexpensive iron catalyst in enhancing the biocrude production from pine, which could be upgraded to better fuel using the HYD process.

Development of Nanofluid-Based Solvent as a Hybrid Technology for In-Situ Heavy Oil Upgrading During Cyclic Steam Stimulation Applications.

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.

In-situ hydrothermal upgrading and mechanism of heavy oil with nano-Fe2O3 in the porous media

Hydrothermal upgrading is a promising technology for heavy oil, yet the impact of reservoir conditions on the catalytic effect of catalysts and the pathway are not clear. In this study, the effect of the formation environment on the catalytic upgrading process was investigated through simulating the reservoir conditions (2000 mD permeability, 25 % porosity) for catalytic hydrothermal cracking of heavy oil. Under the hydrothermal upgrading conditions（240 ℃, 24 h, 50 wt%, 0.1 wt% nano-Fe2O3）, 9.15 % of the heavy component(5.1 % resin and 4.05 % asphaltene) was converted to light component. The content of hydrocarbons below C17 in the saturated fraction increased from 36.29 % to 59.85 %. The structure of the asphaltene was disrupted resulting in a lower level of asphaltene stacking, and NC/NH ratio increased 13.61 % compared to heavy oil. In addition, the reservoir condition with quartz as the supporting medium improved the catalytic ability of iron oxide nanoparticles. When injected into the reservoir medium, nano-size facilitated dispersion on the surface of the proppant and inhibited the aggregation of nanoparticles, which ensured the continuous operation of the active sites on the surface of the catalyst. Electron transfer of Fe2+/Fe3+ catalyzed the heterolytic cleavage of covalent bonds of H2O/heavy oil molecules was the mechanism for heavy oil upgrading. These findings demonstrated the feasibility of in-situ upgrading of heavy oil through the use of nano-catalysts under reservoir conditions.

Effect of biochar-based nano‑nickel catalyst on heavy crude oil upgrading and oil shale pyrolysis

This study involved the preparation of a biochar-based nano‑nickel (Ni/C) catalyst, achieving high dispersion of the nano‑nickel catalyst by utilizing waste coffee grounds as a biochar carrier. The Ni/C catalyst demonstrated commendable catalytic performance in heavy crude oil upgrading. Compared with the control group, the viscosity reduction rate of heavy crude oil was increased by 21.53 %, and the contents of heteroatoms, resins and asphaltenes were effectively reduced, while increasing the ratio of C2-C4 and saturated components. Additionally, the catalyst reduced the initial decomposition temperature and the maximum thermal decomposition rate temperature of oil shale by 10 °C and 8 °C, respectively. The results of DFT calculations also indicated that the catalyst effectively improved the pyrolysis activity of kerogen molecules. Noteworthy characteristics of the catalyst include its low cost, simple operation, and high catalytic activity, making it highly promising for broad applications in unconventional petroleum energy exploitation.

In-situ upgrading of Egyptian heavy crude oil using matrix polymer carboxyl methyl cellulose/silicate graphene oxide nanocomposites

This study delves into catalytic aquathermolysis to enhance the economic viability of heavy oil production by in-situ upgrading technique. It is known that introducing nanocatalysts would promote the aquathermolysis reaction. Therefore, in this study, the effect of matrix polymer carboxyl methyl cellulose/silicate graphene oxide nanocomposites (CSG1 and CSG2) in the catalytic aquathermolysis of Egyptian heavy crude oil was studied. Characterization techniques including Fourier-transform infrared (FTIR), X-ray diffraction (XRD), Dynamic light scattering (DLS), Brunauer–Emmett–Teller (BET) surface area analysis, Scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) were used to evaluate the structure of the synthesized nanocomposites. Results reveal CSG2 has higher crystallinity and superior dispersion compared to CSG1, and both exhibited a good stability in aqueous suspensions. CSG2 enriched with graphene oxide, demonstrates superior thermal stability, suitable for high-temperature applications such as catalytic aquathermolysis process. Single factor and orthogonal tests were used to assess the catalytic aquathermolysis performance of the prepared nanoparticles. The obtained results revealed that the optimum conditions to use CSG1 and CSG2 are 40% water concentration, 225 °C temperature, and 0.5 wt% catalyst percentage. Where, CSG2 showed better viscosity reduction (82%) compared to CSG1 (62%), highlighting its superior performance in reducing the viscosity of heavy oil. Numerical results from SARA analysis, gas chromatography, and rheological testing confirmed the catalytic aquathermolysis's efficacy in targeting asphaltene macromolecules and producing lighter hydrocarbon fractions.

Targeted preparation for hydrocarbons through catalytic hydrodeoxygenation of co-pyrolysis bio-oil using bimetal-loaded Nb2O5 catalyst

The co-pyrolysis of industrial enzymatic hydrolysis of lignin residue with waste plastic to produce bio-oil can increase resource utilization and reduce pollution. However, the high concentration of oxygenated compounds, particularly phenolic compounds, limits the large-scale application of crude bio-oil. Bimetallic-loaded bifunctional catalysts have been prepared by loading different transition metals and Ru onto Nb2O5. We explored their performances in crude co-pyrolysis bio-oil hydrodeoxygenation (HDO). Compared to other transition metals, the selectivities for aromatic hydrocarbons, phenolic compounds, and other oxygenated compounds in the upgraded oil obtained by the catalytic HDO of Ni and Ru bimetallic-loaded Nb2O5 (Ni-Ru@Nb2O5) was the lowest, whereas the aliphatic hydrocarbons selectivity was the highest. The selectivities for other oxygenated compounds, phenolic compounds, and aromatic hydrocarbons in the upgraded oil decreased as the Ni loading increased, whereas the aliphatic hydrocarbons selectivity increased. Ni-Ru@Nb2O5 catalyzed HDO of crude bio-oil showed a maximum selectivity of 86.30 % for hydrocarbons in the upgraded oil at a reaction time of 2 h and a reaction temperature of 280 °C. The degree of deoxygenation of upgraded oil reached 68.87 % under optimal conditions, and the molar ratio of H-to-C was increased from 1.31 (crude bio-oil) to 2.37 (upgraded oil). Ni-Ru@Nb2O5 is an effective catalyst method for the HDO of crude bio-oil.

Kinetic insights into heavy crude oil upgrading in supercritical water

Heavy crude oil upgrading in a supercritical water environment is a promising technology owing to diverse advantages such as heteroatom removal, high yields of low molecular weight fractions, and inhibition of coke production. In order to increase the performance of this process, some challenges need to be overcome by researching the reaction mechanisms and developing proper numerical models. Therefore, the kinetic studies reported in the literature for hydrothermal upgrading of heavy crude oil under supercritical water conditions and their results were systematically analyzed and discussed to achieve a better understanding of the diverse approaches considered to determine the distribution of reaction products and limitations. Additionally, fundamental aspects of the kinetic models, including experimental considerations and numerical methodologies applied for kinetic parameter estimation, are reviewed to obtain representative information about the reactant system that can be subsequently integrated into reactor design models or reservoir simulations.

Electrocatalytic Upgrading of Biomass-Derived Compounds for Biofuel Production

Biomass fast pyrolysis liquid (also known as bio-oil) is considered to be one of the most promising renewable carbon feedstocks. However, fresh pyrolyzed bio-oil is acidic and corrosive and contains large amounts of carbonyl and phenolic compounds produced by polymerization under acidic conditions. This work primarily utilizes an electrochemical conversion strategy using only earth-abundant metal catalysts to achieve the carbonyl hydrogenation process. The results show that upgrading this process produces biofuels with greater stability and higher specific energy. In addition to analyzing the chemical implications of this conversion strategy, this work will also discuss why electrocatalytic conversion is a promising technology path for biofuels and fine chemicals. Reference Huang, S., Lam, C. H.* et al. (2022). "The Structural Phase Effect of MoS2 in Controlling the Reaction Selectivity between Electrocatalytic Hydrogenation and Dimerization of Furfural." ACS Catalysis 12(18): 11340-11354.Huang, S., Lam, C. H.* et al. (2022). "MoS2-Catalyzed Selective Electrocatalytic Hydrogenation of Aromatic Aldehydes in an Aqueous Environment." Green Chemistry.Tu, Q., Lam, C. H.* et al. (2021). "Electrocatalysis for Chemical and Fuel Production: Investigating Climate Change Mitigation Potential and Economic Feasibility." Environmental Science & Technology 55(5): 3240-3249.Garedew, M., Lam, C. H.* et al. (2020). "Greener Routes to Biomass Waste Valorization: Lignin Transformation Through Electrocatalysis for Renewable Chemicals and Fuels Production." ChemSusChem 13(17): 4214-4237. Lam, C. H., et al. (2017). "Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading." Sustainable Energy & Fuels 1(2): 258-266. Figure 1

Valorizing polymeric wastes and biomass through optimized co-pyrolysis for upgraded pyrolysis oil: A study on TG-FTIR and fixed bed reactor

The co-pyrolysis of biomass and polymeric wastes offers a promising approach for waste reduction and valuable product recovery while decreasing fossil fuel dependence. This study aimed to investigate the synergistic effects of blending waste tire (WT) or polystyrene (PS) with sawdust (SD) at varying effective hydrogen/carbon ratio (H/Ceff) on liquid product distribution. Thermal degradation behavior was analyzed using TGA-FTIR, followed by fixed-bed reactor pyrolysis experiments at different temperatures. The devolatilization of SD primarily occurred between 185 and 390°C, while WT and PS decomposed between 250 and 500°C and 350–460°C, respectively. Results showed that SD addition to WT accelerated degradation at lower temperatures. Optimal H/Ceff ratios were 0.42 for WT/SD and 0.64 for PS/SD blends at 500°C, maximizing valued hydrocarbons, reducing pollutants, and yielding the highest liquid fraction. TGA-FTIR analysis revealed the presence of various functional groups, including C-H, CC, CO2, and O-H. The pyrolytic oil showed improved stability with significantly fewer undesired compounds. This research provides theoretical and practical insights into the control and application potential as well as the limitations of high-value energy products derived from the co-pyrolysis of SD, WT, and PS.

Study of heavy crude oil upgrading in supercritical water using diverse kinetic approaches

Heavy crude oil upgrading under a supercritical water environment has demonstrated to have diverse advantages. For commercial applications, it is necessary to develop mathematical models that can predict the reactive behavior of the different components of crude oil under these operating conditions. However, the consideration of different experimental and modeling approaches can significantly influence the determination and evaluation of reaction rates, which complicates providing essential insights into the reaction system and thus generates numerical simulations and strategies that allow for increasing the efficiency of these processes. Therefore, this study analyzes the effect of the supercritical water atmosphere on the diverse reactions among oil components as well as different kinetic modeling approaches reported in the literature to predict the yields of reactive compounds. Complex kinetic models were developed using proposed reaction schemes and experimental data obtained during the upgrading of heavy crude oil under supercritical water conditions. The predictions with the models show good agreement concerning the experimental data. In addition, it was shown that the conversion of asphaltenes to resins and gas compounds under supercritical conditions presents a significant increase in reaction rates compared with experiments under non-catalytic and catalytic thermal cracking conditions.

Novel THAI well arrangements for improving heavy oil recovery rate in comparison to that achievable in the conventional THAI in situ combustion technology

The toe-to-heel air injection (THAI) method is an environmentally friendly process for in situ upgrading of heavy oils and bitumen via in situ combustion (ISC). Unlike the conventional ISC that uses a vertical producer, the THAI process uses a horizontal producer (HP) well to produce the upgraded oil to the surface. Recent field data has shown that the THAI process is a relatively low-oil-production-rate technology. These considerations call for innovative solutions so that the oil production rate is improved, whilst propagating a stable, efficient, and safe combustion front. Consequently, this work has provided those solutions. Through numerical reservoir simulations, using CMG STARS, five completely new THAI well configurations, which have been labeled A01, A02, A03, A04, and A05, have been developed and studied, and their performances are compared against that of the conventional THAI process which has wells arranged in a classic SLD pattern (i.e. the best-performing conventional THAI process) and against each other. The THAI arrangements A02-A04, however, assume a horizontal air injection well, which currently is not used in field practice but may be developed in the future. In field practice, THAI is applied in a line drive configuration starting up-dip and going down on the structure whilst taking advantage of the contribution provided by the drainage due to gravity; the expansion is made one way only (by drilling new patterns in one direction only). For this reason, the classic SLD pattern refers to the case where the dip of the reservoir is significant (>2–3°). However, when the dip of the reservoir is not significant (“flat” reservoirs) there is a possibility to expand the process in both opposing directions. This is the case dealt with in this work. All configurations A01-A05 assume expansion of the THAI commercial operation in both directions. Selection criteria have been developed and used to determine the two best performing processes. For example, in terms of long-term stability, safety, and efficiency of the combustion process, a process named model A01 is the best, as it achieved 99.8% oxygen utilisation when compared with any other model. It also achieves oil recovery, due to two years of combustion only, of 30.78% OOIP, which is greater than that in the base case model. Overall, based on the weighted selection criteria, which are developed from the deepest analyses of the quantitative 1-dimensional time-dependent parameters and from thorough analyses of the qualitative 2-dimensional profiles of temperature, the combustion zone in the form of oxygen mole fraction, and the oil-flow dynamics inside the reservoir in the form of oil saturation, then model A01 is the best and is followed by model A03. The overall performance of each of these two novel methods outweighs that of the conventional THAI process. However, model A03 uses a horizontal well for injection, which is not current field practice. Therefore, future developmental work should concentrate on the novel method A01 for upgrading and recovery of heavy oils and bitumen, especially since this is low-carbon, efficient, wastewater-free, and provides upgrading inside the reservoir and hence it has a low surface footprint.

Experimental investigation on cyclic steam stimulation assisted modified THAI to enhance oil recovery in steam-treated heavy oil

Steam injection is well accepted as a main method for heavy oil reservoirs. Currently, most heavy oil reservoirs have reached the late stage of steam treatment and encountered various challenges thus alternative methods are needed to develop the remaining oil. CSS1 Assisted Modified THAI2 (CSSAMT) is proposed to be an effective follow-up method in heavy oil reservoirs treated by steam. CSSAMT combines the benefits of ISC3 and steam, with steam acting as a protective agent for production wells threatened by combustion as well as a restrainer for oxygen breakthrough. A 3-dimensional physical model was conducted for the experiment to simulate the process and investigate the mechanism. The result demonstrates the feasibility of the CSSAMT process with a high oxygen availability of 99.8% and an average apparent H/C ratio of 0.71, achieving an oil recovery factor of 44.01%. Optimal steam injection parameters were determined as a 0.03 T (dimensionless time)-soak period followed by a 0.06 T production period. Additionally, oil upgrading results were quantitatively described through the carbon number variations, and a prediction formula correlating the sweep efficiency and the carbon number variations was proposed, showing a correlation coefficient of 0.9.

Room temperature catalytic upgrading of unpurified lignin depolymerization oil into bisphenols and butene-2

Lignin is the largest source of renewable aromatics on earth. Despite numerous techniques for lignin depolymerization into mixtures of valuable monomers, methods for their upgrading into final products are scarce. The state of the art upgrading methods generally rely on catalytic funneling, requiring high temperatures, catalyst loadings and hydrogen pressure, and lead to the loss of functionality and bio-based carbon content. Here an alternative approach is presented, whereby the target monomers are selectively converted in unpurified mixtures into easily separable final products under mild conditions. We use reductive catalytic fractionation of wood to convert lignin into iso-eugenol and propenyl syringol enriched oil followed by an olefin metathesis to yield bisphenols and butene-2, thus, valorizing all bio-based carbons. To further demonstrate the synthetic utility of the obtained bisphenols we converted them into polyesters with a high glass transition temperature (Tg = 140.3 °C) and thermal stability (Td50% = 330 °C).

Identification of suitable catalyst among HZSM-5, HY and γ-Al2O3 to obtain upgraded pyrolysis oil with augmented liquid oil yield

This study examines catalytic ability of various zeolite materials in converting discarded tire pyrolyzed oil by employing a moderate sized pyrolysis plant of a 10 L working volume. The study revealed that the yield of liquid fractions using γ-Al2O3 was greater than that of HZSM-5 and HY, while the yield of condensates were limited in the absence of catalyst. The tire waste pyrolysis oil catalytcially enhanced by alumina catalyst analyzed using Fourier transform infrared spectroscopy exhibited the stretching bands corresponding to aromatic and non-aromatic compounds. The GC MS analysis revealed that the cyclic unsaturated fragment percentages in liquids were decreased by the catalysts to 53.9% with HY, 59.0% with γ-Al2O3, and 62.2% with HZSM-5, which in turn was converted into aromatic chemicals. Nitrogen adsorption desorption analysis revealed that γ-Al2O3 has an enhanced surface area of 635 m2/g which improved its catalytic performance. The cracked liquid oil had viscosity (10.36 cSt), values of pour and flash temperatures of −2.2 °C and 41 °C respectively, analogous to petroleum diesel. The upgraded pyrolysis oil (10%) is blended with gasoline (90%), and emission analysis was performed. Moreover, liquid oil needs post treatment (refining) for its use as energy source in transportation application. The novelty of this research is in its comparative analysis of multiple catalysts under controlled conditions using a small pilot-scale pyrolysis reactor, which provides insights into optimizing the pyrolysis process for industrial applications.

Improved concrete via upgraded oil shale ash

Improved concrete via upgraded oil shale ash

Supercritical water upgrading of heavy oil: Effects of reservoir minerals on pyrolysis product distribution

Supercritical water upgrading (SCWU) is a promising technology for heavy oil recovery and refining, in which minerals could act as catalysts, but the effect on the upgraded product distribution remains unclear. In this study, heavy oil upgrading experiments in supercritical water (SCW) were carried out at 400°C and 25 MPa to investigate the effects of reservoir minerals such as quartz, carbonate, feldspar and clay minerals on the upgrading process. The result indicated that carbonate minerals and clay-bearing minerals produced noticeable benefits to the SCWU of heavy oil process. In carbonate minerals, dolomite showed the strongest catalytic effect in promoting hydrothermal cracking of hydrocarbon macromolecules, with a 5.6 % reduction in heavy fraction and a 12.2 % increase in light fraction of the upgraded oil. Clay-bearing minerals mainly exhibited oil-enhancing and coking-inhibiting benefits, calcium montmorillonite exhibited the most significant increase in oil production of 9 %, while zeolite most significantly reduced the coke activation energy by 62 %. Regarding the catalytic mechanism, the catalytic effect of carbonates originated from the MgO and CaO sites on the surface. For clay minerals, the acidic catalytic sites exist in the interlayer domains of montmorillonite and in the pores of zeolite provided higher catalytic efficiencies in oil production. This study demonstrated the feasibility of using natural minerals as inexpensive catalysts for supercritical water upgrading of heavy oil.