Petroleum Residues Research Articles

Fingerprinting of Weathered Oil Residues from the Deepwater Horizon Oil Spill: The Importance of Multiple Lines of Investigation

ABSTRACT 2017-189 The crude oil released from the Macondo Well, also known for its location in Mississippi Canyon area as the MC252 well during the Deepwater Horizon Oil Spill, entered an environment already containing a complex mixture of hydrocarbons from both natural and anthropogenic sources, many of which have closely related chemical profiles. To understand the impact of the released oil in offshore areas, a method was needed to distinguish MC252-related hydrocarbons from other sources. A multiple lines of evidence approach was developed to identify weathered MC252 oil in offshore sediments in the Gulf of Mexico. Chemical data for alkanes, PAH, petroleum biomarkers and metals were combined with spatial, temporal, and observational information to examine the fingerprints for more than 4,000 sediment samples collected over the span of five years. The unique conditions of the Gulf of Mexico (GOM), with many natural petroleum seeps and tepid seas, provided an ideal environment to support microbial degradation of petroleum. As a result of these conditions, the initial fingerprint of the MC252 was rapidly and extensively altered in the environment including depletion of petroleum biomarkers, usually assumed to be recalcitrant and often used in ratios to identify petroleum residues. Revised biomarker match criteria were defined to account for biodegradation within this fraction. Applying this methodology to the offshore sediment data from the GOM provided a comprehensive understanding of the distribution of the MC252 oil in offshore sediment and an understanding of the various transport pathways which conveyed the oil to the sediments.

Hydrogen production by catalytic gasification of petroleum residue

ABSTRACTThe liquid fuel gasification to obtain a clean flue gas for power generation and produce chemicals such as methanol is a most promising attempt to reduce the greenhouse gas emissions and air pollutants. In this paper, an equilibrium model of liquid fuel gasification was developed by the method of Gibbs free energy minimization. Two kinds of catalysts: Ni/CeO2/Al2O3 and Ni/Al2O3 were used to explore the influence of catalysts and operating conditions on hydrogen yield and char conversion. Over the ranges of operating conditions studied, the maximum hydrogen yield reached 52.47 vol%, whereas the char conversion varied between 45.2% and 98.5%. The results indicated that an appropriate reaction temperature is favorable for higher hydrogen production and char conversion. The model was validated with experimental data obtained from a fluidized bed gasifier.

Effect of mixing and vapor residence time on thermal cracking of bitumen in a Mechanically Fluidized Reactor

Fluid Coking™ is a non-catalytic carbon rejection process that is utilized to convert petroleum residues into more valuable light and middle distillates. In this process, heavy oil is sprayed into a fluidized bed of hot coke particles; the liquid heats up and undergoes endothermic thermal cracking to vapors, non-condensable gas and solid coke. This study shows that liquid distribution on hot coke particles affects the products yields and the liquid product quality. The vapor residence time also affects the products yields and the liquid product quality.The Mechanically Fluidized Reactor has been successfully developed and implemented for Fluid Coking applications. Multiple vapor phase residence times can be investigated simultaneously while reducing intrinsic errors present in a complex system such as coking. The impact of applied bed mixing and vapor phase cracking on Fluid Coking yields, as well as on product oil quality can, thus, be accurately evaluated.Applying mechanical mixing to the bed of coke particles results in better liquid distribution on coke particles and reduces coke yields. It also increases the yield of low viscosity, low molecular weight liquid at short vapor residence times. At long vapor phase residence times, however, vapors crack to gas, resulting in a concentration of higher viscosity, higher-molecular weight compounds in the liquid phase. The additional vapors that are produced in the bed thanks to enhanced mixing are more reactive and easily crack to gas at long vapor residence times. Realizing the full benefit of enhanced liquid distribution therefore requires minimization of the vapor residence time.

Flow investigation in an industrial-scale soaker using radiotracer technique

Flow dynamics of heavy petroleum residue in an industrial-scale soaker operating in a petroleum refinery was investigated. Residence time distributions (RTDs) of the residue were measured using radiotracer technique. Bromine-82 as dibromobiphenyl was used as radiotracer for tracing the petroleum residue. The measured RTDs were treated and mean residence times (MRTs) were determined. The measured RTD data was simulated using a combined model i.e. axial dispersion model in parallel with tanks-in-series with stagnant volume and exchange. The results of the model simulation fitted very well to the experimentally measured data and identified bypassing or existence two parallel flow paths within the soaker.

Molecular Evolution of Asphaltenes from Petroleum Residues after Different Severity Hydroconversion by EST Process

Residue conversion processes are becoming increasingly important in the world today, because of several market and economic factors. The residues contain a large mass fraction of heavy and polar compounds known as asphaltenes, which can cause major problems in the conversion processes. Heavy feedstocks with high asphaltene content can become an economic opportunity if they can be converted to lighter products. In this perspective, Eni has developed a process called EST (Eni Slurry Technology) to convert very heavy feedstocks into high quality transportation fuels. In the course of the EST process, the asphaltene molecules are converted to smaller fractions, enhanced to fuels; the unconverted fraction is recycled in the reactor and treated again and again. The technology is based on a very active, dispersed, nonaging slurry catalyst, which prevents coke formation and promotes upgrading reactions (sulfur, nitrogen, and metal removal and Conradson carbon residue (CCR) reduction). Knowledge of the asphaltene ...

Characteristics of the ignition of organic coal–water fuels for boiler installations

The ignition processes of organic coal–water fuels (OCWFs) in the flow of a heated oxidant (temperature, 700–1000 K; velocity, 0.5–5 m/s) were studied. The experiments were carried out with the small single drops of OCWFs (radii, 0.2–0.5 mm), which correspond to the injection devices of typical boiler installations. The component base of the test composition fuels included B2 brown coal, typical waste coals (the filter cakes of G and D coals), spent motor and transformer oils, and petroleum residue. The influence of the component composition (the properties and concentrations of solid and liquid combustible components) on the characteristics of the initiation of the combustion of single OCWF drops was found. The dependences of the delay times of ignition and complete combustion on the temperature of an oxidant and on the drop sizes of OCWFs were determined. It was established that, at maximum oxidant temperatures (above 900 K) and minimum drop sizes (smaller than 300 μm), difference between the integral characteristics of ignition was sufficiently small (smaller than 10%) for the fuels prepared from components with substantially different properties.

On the catalysis capability of transition metal oxide nanoparticles in upgrading of heavy petroleum residue by supercritical water

Vacuum residue cracking has been successfully conducted under supercritical water condition in presence of various metal oxide nanocalysts, namely NiO, CuO, ZnO, Co2O3, and Cr2O3 synthesized at supercritical water. The cracking experiments were carried out at 450°C. Three species of cracking: maltene, asphaltene, and coke were then weighed and their corresponding speciation was defined. Gas chromatography-mass spectrometry (GC–MS), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), and elemental analysis (CHNS) tests were utilized to prove the performance of upgrading reactions. It was revealed that NiO showed the best performance among other catalyst, in which its activity and stability in catalytic cracking changed slightly. According to the results obtained from GC–MS, NMR, TGA, and CHNS anlyses, it was confirmed that the proportion of heavy hydrocarbons of products (i.e. non-catalytic and catalytic reactions) was lower than that of feedstock.

Coke and radicals formation on a sulfided NiMo/γ-Al2O3 catalyst during hydroprocessing of an atmospheric residue in hydrogen donor media

Coking on catalyst during hydroprocessing of petroleum residues is an important issue that should be addressed for better catalyst performance. This paper studies reaction and coking behaviors of Maoming atmospheric residue (AR) over a sulfided commercial NiMo/γ-Al2O3 catalyst in the presence and absence of a hydrogen donor solvent, tetrahydronaphthalene (THN), in a micro-reactor at temperatures of 400–460°C and reaction time of 0–60min. It reports the changes in yields of CS2 soluble matter (CS2-S), CS2 insoluble matter (coke) and gas, as well as the changes in quantity of coke on the catalyst and in radical concentration of the reaction system, coke on catalyst and CS2-S. It is found that compared with the changes in yields, which are significant at temperatures higher than 420°C, the changes in radical concentration are significant at 400°C. The catalyst promotes hydrogen donation of THN, which lowers the amounts of coke formed in the liquid phase, on the catalyst, and the activation energy of coking on the catalyst.

Characterization of Petroleum Residues with Varying Cutting Depth and Corresponding Vacuum Distillates Derived from Laboratory Deep-Vacuum Fractionation of Unconventional Heavy Oil for an Instructive Utilization Guideline

Petroleum residues with varying cutting depth and corresponding vacuum distillates have been prepared from laboratory deep-vacuum fractionation using unconventional heavy oil (UHO) originated from Venezuela first. They are then sequentially characterized by general analysis, process analysis, and pyrolysis analysis with thermogravimetric analysis (TGA), derivative thermogravimetric analysis (DTG), and differential scanning calorimetry (DSC). Results indicate that a greater increase in distillates recovery would be expected in the case of UHO than that of other referenced crudes under the same cut temperature and stand a good chance to make refineries involved with UHO get comfort by partially offsetting the shortage of light distillates. From the view of structural composition characteristics, cuts, even the ones with high cut temperature, have a high chance of cracking into compounds with lower molecular weight during conversion. Notably, in the case of +565 °C petroleum residue (R5), except for the endo...

Meliorate optical textures and mesophase contents by promising approach of deasphalting of petroleum residues

The aim of this work is to study melioration in mesophase formation behaviour by deasphalting of petroleum residues. Pitches prepared from VRs have undesirable high values of physico-chemical properties as compared to their corresponding DAOs pitches. This is due to presence of high molecular weight asphaltenes molecules in VRs. The optical microscopic images of VR-390-1 and VR-390-2 pitches showed that they have small sized, distorted and agglomerated types of mesophase having mesophase contents (MC) 25 vol% and 22 vol% respectively but deasphalting of these VRs improve the growth and optical texture of mesophase in DAO-390-1 (29 vol%) and DAO-390-2 (35 vol%).

Interpreting Interactions between Ozone and Residual Petroleum Hydrocarbons in Soil.

We evaluated how gas-phase O3 interacts with residual petroleum hydrocarbons in soil. Total petroleum hydrocarbons (TPH) were 18 ± 0.6 g/kg soil, and TPH carbon constituted ∼40% of the dichloromethane-extractable carbon (DeOC) in the soil. At the benchmark dose of 3.4 kg O3/kg initial TPH, TPH carbon was reduced by nearly 6 gC/kg soil (40%), which was accompanied by an increase of about 4 gC/kg soil in dissolved organic carbon (DOC) and a 4-fold increase in 5-day biochemical oxygen demand (BOD5). Disrupting gas channeling in the soil improved mass transport of O3 to TPH bound to soil and increased TPH removal. Ozonation resulted in two measurable alterations of the composition of the organic carbon. First, part of DeOC was converted to DOC (∼4.1 gC/kg soil), 75% of which was not extractable by dichloromethane. Second, the DeOC containing saturates, aromatics, resins, and asphaltenes (SARA), was partially oxidized, resulting in a decline in saturates and aromatics, but increases in resins and asphaltenes. Ozone attack on resins, asphaltenes, and soil organic matter led to the production of NO3-, SO42-, and PO43-. The results illuminate the mechanisms by which ozone gas interacted with the weathered petroleum residuals in soil to generate soluble and biodegradable products.

Mathematical modeling of unsteady-state gasification of petroleum residue

ABSTRACTGasification is a thermochemical process which converts organic fuels into a high caloric value syngas and other chemicals in the presence of a gasification agent. Tar generation represents the strongest barrier for the use of fixed-bed reactors for liquid fuel gasification, whereas sufficing is only possible with catalytic activities and expensive physical processing. In this work, a kinetic model of waste oil gasification was proposed which can be used a flexible model to provide a quantitative prediction of product yield of other fuels. Results were validated against the experimental measurements and showed a good agreement. In accordance with the modeling results, it was found that the greenhouse gas emission (GGE) of waste oil is higher than that of biomass materials, but the caloric value of the syngas generated is higher. The residence time was also recognized as an important design parameter to improve the syngas volume fraction.

MOLECULAR DIAGNOSTIC RATIOS TO ASSESS THE APPORTIONMENT OF PETROLEUM HYDROCARBONS CONTAMINANTION IN MARINE SEDIMENT

As maritime fulcrum nation, in Indonesia, marine environmental analytical chemistry field is still under developed. So that why, this review paper aims to provide basic understanding of the use some molecular diagnostic indices using n-alkanes indexes and polycyclic aromatic hydrocarbons (PAHs) diagnostic ratios to estimate the source of apportionment of the hydrocarbons contamination and origin. The n-alkane chromatograms were then used to characterize the predominance of petrogenic or biogenic either terrestrial or aquatic. Furthermore, characterization allowed to discriminate riverine versus marine input. The occurrence of a broad unresolved complex mixture can be an evidence of biodegraded petroleum residues. For aromatic compounds, the prevalence of petrogenic, pyrolitic, and combustion-derived can be easily plotted by using isomers ratio calculation. This paper thus provides useful information on the hydrocarbon contamination origin, especially in marine sediments. Further researches should be undertaken in order to validate the use of molecular diagnostic ratio with isotopic approach.

High-Melting Point Asphalt on the basis of High-Paraffin Oil Tar

Objectives: A special place among oil bitumen is occupied by refractory bitumen - bitumen of solid marks or, as they are called, solid bitumen. Methods: They differ from the liquid bitumen with high softening point and some other physical and chemical properties, conditioned by the technological mode of production. Bitumen of solid brands find their application in various sectors of the economy both in pure form, as the basic raw material, or as a mixture with various organic products and minerals as part of the production of a number of technical materials. Results: The positive qualities of refractory bitumen and asphaltites, making them indispensable for heat and water proofing of underground channel-free heat conductors are: high softening point; thermo plasticity, which excludes the appearance of cracks; watertight; low water absorption (up to 30 times less than bitumen perlite). The possibility of obtaining high-melting grades of bitumen from high-paraffin tar in the presence of a catalytic complex by “conventional oxidation” that is the raw material purge air, and without purging air using potassium permanganate as a source of molecular oxygen. It is shown that in “conventional oxidation” (sparing of oxygen of air) in the presence of a catalyst complex it is possible to achieve a high softening temperature - over 1000C - almost four times faster than using air purging without purging catalyst. Applications: Using the catalyst of atomic oxidation of petroleum residues showed that it took about 7 hours to reach the softening temperature of almost 1300C

Supercritical Fluid Extraction of Fluid Catalytic Cracking Slurry Oil: Bulk Property and Molecular Composition of Narrow Fractions

The supercritical fluid extraction and fractionation (SFEF) method has the capacity of separating heavy petroleum residue into fractions with different processabilities. Different from traditional heavy residue feedstock, slurry oil (SLO) is a heavy liquid product from the fluid catalytic cracking (FCC) process, and there is concern for its potential application in producing carbonaceous materials. The high-value utilization of FCC SLO depends upon the aromatic and contaminate contents in the feedstock. The present study aimed to extend the SFEF method to the FCC SLO system and investigate the property and molecular composition distribution of derived fractions. A FCC SLO was subject to the SFEF process and separated into 13 extract fractions with each 5 wt % yield and 1 unextracted end cut. Systematic bulk property measurements, including boiling point distribution, density, molecular weight, viscosity, and carbon residue, were performed on each fraction. Hydrocarbon molecules in different fractions were...

Effects of residence time and heating rate on gasification of petroleum residue

ABSTRACTGasification of petroleum residue has been considered as the potential technology due to the advantages of converting the liquid fuels into syngas using partial oxidation. In this paper, we developed a one-dimensional kinetic model to simulate the effects of residence time and heating rate on the gasification characteristics. Results showed that gasification under higher heating rate improves the hydrogen yield and carbon conversion efficiency. It was also found that the residence time plays a major role in the process; higher residence time improves the hydrogen yield and gasification efficiency. The model was validated against the reported data and found to be in good agreement.

석유계 잔사유 및 coal-tar의 핏치 개질 특성

석유계 잔사유 및 coal-tar의 핏치 개질 특성

CFD simulation of entrained-flow gasification of liquid fuels

In this study, a CFD model of entrained-flow gasification of petroleum residue proposed to simulate the effects of some critical parameters such as equivalence ratio and system pressure on carbon conversion efficiency, tar yield, hydrogen concentration, and higher heating value of the syngas. It is a 2D model and steady state, which can be used as a general model to evaluate the performance parameters of other fuels (coal, biomass, and municipal solid wastes) during gasification process. Results showed the equivalence ratio has a negative effect on the higher heating value of the syngas and a positive impact on the gasification efficiency. It also found that the carbon conversion efficiency strongly depends on the equivalence ratio and gasification temperature. The model validated against experimental observations and found to be in good agreement.

Sources and mass inventory of sedimentary polycyclic aromatic hydrocarbons in the Gulf of Thailand: Implications for pathways and energy structure in SE Asia

Surface sediments obtained from a matrix of 92 sample sites in the Gulf of Thailand (GOT) were analyzed for a comprehensive study of the distribution, sources, and mass inventory of polycyclic aromatic hydrocarbons (PAHs) to assess their input pathways and impacts of the regional land-based energy structure on the deposition of PAHs on the adjacent continental margins. The concentration of 16 PAHs in the GOT ranged from 2.6 to 78.1ng/g (dry weight), and the mean concentration was 19.4±15.1ng/g. The spatial distribution pattern of 16 PAH was generally consistent with that of sediment grain size, suggesting the influence of regional hydrodynamic conditions. Correlation and principal component analysis of the PAHs indicated that direct land-based inputs were dominantly responsible for the occurrence of PAHs in the upper GOT and the low molecular weight (LMW) PAHs in the coastal region could be from petrogenic sources. A positive matrix factorization (PMF) model apportioned five contributors: petroleum residues (~44%), biomass burning (~13%), vehicular emissions (~11%), coal combustion (~6%), and air–water exchange (~25%). Gas absorption may be a significant external input pathway for the volatile PAHs in the open GOT, which further implies that atmospheric loading could be important for the sink of PAHs in the open sea of the Southeast Asia (SE Asia). The different PAH source patterns obtained and a significant disparity of PAH mass inventory in the sediments along the East and Southeast Asia continental margins can be ascribed mainly to different land-based PAH emission features under the varied regional energy structure in addition to the depositional environment and climatic conditions.

Light Products and H2-Rich Syngas over the Bifunctional Base Catalyst Derived from Petroleum Residue Cracking Gasification

Vacuum residue is utilized by a process involving the residue cracking and coke gasification regeneration. In this process, vacuum residue is first converted into the products of light olefins and light oils by catalytic cracking, and then the cracking-generated coke is gasified into H2-rich syngas by using a bifunctional base catalyst. Their cracking gasification effects of vacuum residue are studied in a dual fluidized bed reactor. The results show that the solid base catalysts could enhance light olefin yield (have high olefinicity) and inhibit the formation of coke in comparison with silica sand and a hydrothermal treatment zeolite catalyst (FCC catalyst). Furthermore, the catalyst prepared at a CaO/Al2O3 molar ratio of 12:7 displayed a better cracking effect than the one produced at the molar ratio of 1:1. The effects of the reaction temperature and the catalyst-to-oil ratio on the distribution of cracking liquid from vacuum residue solid base cracking are discussed. The results showed that the heavy...