Petroleum Residues Research Articles

Advances in Upgrading Process of Petroleum Residue: A Review

Due to the depletion of light crude oil reserves, heavy crude oil and residues are the alternatives to meet ‎the ‎increasing global demand for light oil products. Heavy crude oil and residues are characterized by the presence of heavy ‎hydrocarbon ‎compounds which contain high levels of impurities such as metals, nitrogen, and sulfur-containing compounds. ‎Methods of ‎upgrading are required to increase refining efficiencies and to obtain high-quality products.‎ Upgrading processes can be categorized into three categories; ‎carbon rejection processes, hydrogen addition processes, and a combination of the two. The catalyst can be used with any of these processes for better improvement. Many types of research have been carried out to develop a high-performance process which is stable, high commercial products yield, and low solids formation. In this work, recent advances on petroleum residues upgrading with catalyst, solvents, and thermal cracking were reviewed. Advantages and disadvantages of each process were discussed along with conditions and main features. Nanoparticles catalysts and supercritical fluids based-processes are the trends of upgrading due to the excellent performance of these processes.

Advances in Upgrading Process of Petroleum Residue: A Review

Due to the depletion of light crude oil reserves, heavy crude oil and residues are the alternatives to meet ?the ?increasing global demand for light oil products. Heavy crude oil and residues are characterized by the presence of heavy ?hydrocarbon ?compounds which contain high levels of impurities such as metals, nitrogen, and sulfur-containing compounds. ?Methods of ?upgrading are required to increase refining efficiencies and to obtain high-quality products.? Upgrading processes can be categorized into three categories; ?carbon rejection processes, hydrogen addition processes, and a combination of the two. The catalyst can be used with any of these processes for better improvement. Many types of research have been carried out to develop a high-performance process which is stable, high commercial products yield, and low solids formation. In this work, recent advances on petroleum residues upgrading with catalyst, solvents, and thermal cracking were reviewed. Advantages and disadvantages of each process were discussed along with conditions and main features. Nanoparticles catalysts and supercritical fluids based-processes are the trends of upgrading due to the excellent performance of these processes.

Influence of reaction pressure on co-pyrolysis of LDPE and a heavy petroleum fraction

Pyrolysis of waste plastics to recycle valuable hydrocarbons represents an attractive technology for reducing waste and providing feedstocks for petrochemical products and fuels. Via the simultaneous processing of heavy petroleum residue fractions, synergies can be harnessed by converting bottom-of-the-barrel refining products into lighter fractions with higher value while improving processability of plastic waste materials. To investigate the effect of reactor pressure, a continuous laboratory co-pyrolysis plant was operated. The setup consisted of two consecutive tubular zones to convert a mixture of LDPE and a heavy petroleum residue to a final temperature of 450 °C at different pressures between 2 and 10 bar. The products were evaluated regarding obtained mass yields and their boiling range. Gaseous and liquid products increased with enhanced pressure, resulting in nearly tripled gas and light liquid formation, whereas more unconverted feed was consumed. Because the reactor pressure also affects the residence time by suppressing evaporation, which subsequently varies between 360 and 440 s, further investigations considering the dependence of product yields on the residence time over a range of 280 to 480 s were necessary. The comparison resulted in the conclusion that the enhancing effect of increased reactor pressure is not only caused by a retention time elongation in the hot reactor zone. Other physical effects also play a role, such as promoted heat transmission and a direct intervention of reactor pressure with the chemical reactions. In the tested range, an enhancing effect of higher reactor pressures on the cracking of the reaction mixture was observed. These novel experimental results indicate, that conversion toward lighter cracking products can be increased by pressure adjustments and highlights that the pressure should be included in process optimizations.

Facile Preparation and Characterization of Carbon Fibers with Core-Shell Structure from Graphene-Dispersed Isotropic Pitch Compounds.

In this study, isotropic pitch-based carbon fibers were prepared from a mixture of petroleum residue and graphene nanoplatelets with different contents. The softening point and synthetic yield of synthesized isotropic pitches were analyzed and compared to characterize the nature of the pitches. The surface and thermal characteristics of the fibers were observed using scanning electron microscopy and thermogravimetric analysis (TGA), respectively. From the results, it was observed that the prepared carbon fibers had an interesting core-shell structure. In the TGA analysis with air, the carbon fiber having 0.1 wt.% of graphene showed a higher residue yield than that of the sample having 1.0 wt.% of graphene. This result can be explained due to the graphene being placed on the surface region of the carbon fibers and directly helping to increase the surface area of the carbon fibers, resulting in rapid oxidation due to the enhanced contact area with oxygen.

Processing of Heavy Petroleum Residues by Filtration Combustion

A process flow diagram has been developed for two-stage disposal of waste, generated by deep processing of heavy petroleum residues (HPR), using the filtration combustion method to obtain heat as the final product, and optimal processing conditions have been determined. The first stage is the HPR gasification process to produce a combustible aerosol consisting of a low-calorific-value gas with a heat of combustion of about 1.4 MJ/m3 and fine droplets in an amount of up to 80% of the mass of HPR fed and similar to HPR in composition. At the second stage, the aerosol was burned to produce heat. Options for the disposal of the heavy petroleum residues as received and the same with a carbon fuel admixture (up to 5%) have been considered. It has been found that the addition of carbon fuel helps to stabilize the combustion front.

Hydrothermal liquefaction of Scenedesmus abundans biomass spent for sorption of petroleum residues from wastewater and studies on recycling of post hydrothermal liquefaction wastewater

In this study Scenedesmus abundans was used as a biosorbent material for removing hydrocarbons from simulated petroleum wastewater. Batch experiments resulted in the removal of 92.16% of hydrocarbons from simulated wastewater within 60 min. The spent biosorbent was converted to bio-oil through hydrothermal liquefaction process (HTL) at temperature range from 220 to 320 °C with 1 h holding time. Liquid hydrocarbons (bio-oil) yield was 43.4 wt% at 300 °C with 15 g of spent sorbent loading and possessed HHV of 39.10 MJ/Kg. Additionally the HTL wastewater (aqueous phase) was recycled as reaction medium and studied for its effects on bio-oil yield which increased till second cycle (47.91 wt%). HTL bio-char was employed as adsorbent to remove heavy metals from wastewater. It showed greater removal efficiency of 86.5% to Ni(II) ions. From the results it was concluded that the petroleum residues can be effectively recycled back into liquid hydrocarbons with simple waste management pathway.

The Role of Zeolite Catalysis in Modern Petroleum Refining: Contribution from Domestic Technologies

The problems of zeolite catalysis associated with the introduction of domestic technologies are considered. Particular attention is paid to works related to the use of alternative components of catalytic systems, the introduction of new environmentally friendly materials that improve the quality of the fuels produced with their use. The processes of catalytic cracking, processing of heavy petroleum residues, solid-acid alkylation, and synthesis of light olefins and the problems of renewable feedstock processing are discussed in detail.

SURFACE AND ADHESION PROPERTIES STUDY OF PROPHYLACTIC LUBRICANTS BORDER LAYERS ON METALLIC SURFACE

This study is aimed the developing the special petroleum products, namely, preventive lubricants (PL) used in the field of solid minerals transportation. The surface and adhesion characteristics of the prophylactic compositions developed earlier on the basis of thermodestructive and thermocatalytic processes products of oil refining are investigated. It is set that the prophylactic agents contain the far of surface active substances, such as resins, pyrobitumens and other polyaromatic hydrocarbon compounds: in the heavy gas-oil of the catalytic cracking their content is above 45.96 %, in an easy gas-oil – 15.07 %, that results in the improvement of viscosity-temperature properties of products and promotes their oiling ability. The basic amount of compounds with high superficial activity is contained in heavy fractions of oil, and in the process of processing concentrated in a petroleum residue - petroleum tar that was used as depression addition in mixtures of prophylactic agents. For protecting of metallic surfaces of mountain transport from a direct contact with the transported material in the conditions of the lowered temperatures it is recommended to apply composition of the catalytic cracking mixtures with content of petroleum tar from 2 to 5%. <span style="opacity: 0;"> . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . </span>

Heteroatom Removal as Pretreatment of Boiler Fuels

Heteroatom removal without the use of hydrogen was investigated for the pretreatment of heavy fuels to produce cleaner burning boiler fuels from petroleum residua and coal. This is relevant for app...

Composition of Diesel Fractions Produced by the Semicoking of Kukersite Shale in Different Equipment

By chromatography and mass spectroscopy, industrial diesel fractions of tar obtained by the semicoking of Kukersite shale in a Kiviter gas generator and a Petroter-1 solid-fuel system are analyzed. The content of groups and types of compounds in the samples is compared. In the Petroter-1 fraction, the content of naphthenes (1.7%), dienes (2.6%), indenes (22.1%), ketones (7.3%), and furans (3%) is about twice that in the Kiviter fraction. In the Kiviter fraction, the content of paraffins (17.4%), olefins (19%), alkylbenzenes (23%), and naphthalenes (16.1%) is higher by a factor of about 1.3. The presence of oxygen-bearing compounds in the flue oil permits satisfactory solution of the tars and asphaltenes of the petroleum residues and decrease in their pour point. In other words, the performance of petroleum fuel-oil is significantly improved.

Scientific and Practical Aspects of Bitumen Emulsion Mastic Creation

It is interesting to consider the possible application as an alternative raw material in the manufacture of bituminous emulsion material residual bitumen grade BNN 80/120, production technology which implies a significant reduction in the proportion of paraffinic hydrocarbons by allocating them in the oil fractions in the evacuation of heavy petroleum residues. As a raw material in the production of BEM they should use the bitumen obtained from the heavy oils of naphthenic aromatic base with a minimum content (up to 2% by weight) [1] of high-molecular straight-chain paraffinic hydrocarbons (P-HC), whose reserves are largely limited and difficult to access. In this regard, the expansion of the raw material base of bitumen production due to the involvement of HOR resinous paraffin base confirms the relevance of the studies. The difficulties in the production of insulating BEMs, that meet the requirements of GOST 30693-2000 on the basis of oxidized HOR paraffin base, are explained by the fact that protective coatings (PK) from such materials with the decrease in the glass transition temperature (point) are characterized by an increased intensity of internal stress (δv) in the volume of BEM, in which the increase of the strength growth intensity (δp) occurs, so premature spontaneous destruction occurs in the process of oxidative destruction, i.e. in the conditions of their operation. This is explained by the fact that at the temperatures above Tst, highly elastic and plastic deformations develop in bitumen, and internal stresses relax easily. With decreasing Tst, the rigidity of bitumen increases sharply, the relaxation processes decelerate, and internal stresses increase substantially.

Modeling of atmospheric and vacuum petroleum residue hydroconversion in a slurry semi-batch reactor: Study of hydrogen consumption

In this work, Arabian light atmospheric residue and Safaniya vacuum residue were hydroconverted in a slurry phase semi-batch stirred tank reactor at 15 MPa for a wide range of temperatures (420–440 °C) and reaction times up to 4 h. Experimental data was used to develop a semi-batch reactor model including vapor-liquid equilibrium, gas-liquid mass transfer and gas phase hydrodynamics. Mass transfer and kinetic parameters were estimated by minimizing not only the total masses of products but also the outlet gas flow dynamics. Mass transfer and hydrogen consumption were compared against former studies using a batch reactor, a continuous stirred tank reactor and work by other authors, reported in the literature. Higher hydrogen consumption was achieved with the semi-batch reactor and no hydrogen mass transfer limitation was observed. Therefore, it was concluded that this setup is more suited and reliable for studying the chemical kinetics of slurry-phase hydroconversion of petroleum residues and permits improved representation of the role of hydrogen compared with current models.

Utilization of bifunctional catalyst for upgrading petroleum residue via cracking and gasification: Effect of catalysts

Vacuum residue is stepwise and high-efficient converted by the base cracking and coke gasification process. Cracking effect of vacuum residue was carried out with different bifunctional catalysts in a fluidized bed reactor, respectively. Calcium aluminate catalyst specialized for cracking and gasification procedure is selected with the activities of cracking and gasification. In comparison with silica sand, calcium aluminate catalyst showed the higher vacuum residue cracking activity, and cracking activity gradually increased with increasing the Ca/Al ratios. The results indicated that C2C4 olefinicity of above 60.4%, cracking-generated coke of about 5.0 wt%, and light oil yields is over 84.0 wt% at 650 °C with a catalyst-to-oil ratio of 7.0. Moreover, it was also found that calcium aluminate catalyst synthetized with the Ca/Al molar ratio of 12:7 and carbon black as pore-forming agent displayed a better cracking properties than that of the other catalysts. VR cracking properties over calcium aluminate catalysts was closely related to their basicity, as indicated by the Hammett indicators method. Cracking-generated coke on the base catalyst was well gasified with pure steam at 800 °C and produced the syngas with the total content of H2 and CO2 up to 81.5 vol%, the coke conversion over the tested catalysts is of above 93.6% in 30 min. Also, the alternating base cracking and gasification operations were performed three times to verify the stability of the optimal calcium aluminate catalyst. The selected catalysts presented high hydrothermal stability and stable cracking activity, which could be potentially used for vacuum residue stepwise and high-efficient utilization via vacuum residue catalytic cracking and gasification regeneration process.

Thermogravimetry applied for catalytic degradation of atmospheric residue of petroleum on mesoporous catalyst

Thermogravimetry was used in order to evaluate thermal and catalytic degradation of atmospheric residue of petroleum (ATR) which is found at Brazilian refineries, after a process of atmospheric distillation. The catalyst used for the thermocatalytic degradation of ATR was the AlMCM-41 mesoporous material. The AlMCM-41 was obtained from hydrothermal method using cetyltrimethylammonium as organic template. The calcined material was characterized by chemical analysis and X-ray diffraction. The thermogravimetry analysis was carried out at temperature range of 30 to 900 °C and heating rates of 5, 10 and 20 °C min−1, under nitrogen gas. From TG, the activation energy, determined using the Ozawa–Flynn–Wall kinetic method, decreased from 288 kJ mol−1, for pure ATR, to 55 kJ mol−1, in the presence of the AlMCM-41 material, evidencing the efficiency of the mesoporous materials for the catalytic degradation of petroleum residues.

Improved thermogravimetric system for processing of oil sludge using HY zeolite catalyst

The oil sludge residue presents an aggregate of hydrocarbons, organic and inorganic impurities, and water. The microporous and mesoporous zeolites are considered promising catalysts for processing of petroleum residues generated in refining processes. The aim of this work was to study the degradation of petroleum sludge obtained from primary processing, with applications of an improved thermogravimetry system and HY zeolite, at specific temperature ranges and degradation times, in order to obtain light gases and distillate fuels. The NaY zeolite was synthesized under hydrothermal treatment of a gel containing sodium silicate, sodium aluminate, and water. The obtained solid material was filtered, dried and calcined, and then ion-exchanged with ammonium chloride and calcined in order to obtain its protonic acid form (HY). The samples’ characterization by TG/DTG, XRD, and SEM proved that the crystalline structure of the faujasite zeolite was obtained. The thermal and catalytic degradation of the petroleum sludge was performed with 1.0 g of sample containing 10% of HY zeolite in the temperatures of 100, 200, 300, 400, and 500 °C, varying the time from 0 to 60 min to each temperature, using an oven with temperature program system, adapted with a Shimadzu precision balance. The curves obtained with this system evidenced that the presence of HY zeolite improves the degradation of the residue, with decreasing of the activation energy for the processes, as determined using the Arrhenius model.

Thorough assessment of delayed coking correlations against literature data: Development of improved alternative models

The predictability of the existing and some improved correlations were evaluated against the available largest dataset for the prediction of the product yields from delayed coking, such as, coke, liquid, gas, gas oil, naphtha, heavy gas oil, liquid sulfur content as well as API vs. CCR. Except for some cases where the relationships of Volk et al. and Castiglioni and the simplistic models of Maples, and Gary–Handwerk predicted somewhat appropriately, the existing models failed in most of the cases. The alternative models contained seven independent variables including three feedstock properties and four operating conditions. Overall, the developed correlations accounted for higher than 86% of the variances. The quality of the regressions followed the order of naphtha < dry gas < distillate < liquid sulfur content < heavy gas oil < coke < gas oil with the maximum correlation coefficient of 96.7%. The weighted absolute percentage errors with the alternative relationships of total gas oil, heavy gas oil, liquid sulfur content, and distillate were smaller than 11.12%, indicating the good predictability of the models. The new models can then be recommended for application over a wide range of operating conditions with various types of heavy fuel oils and petroleum residues.

Source-specific lung cancer risk assessment of ambient PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) in central Tehran

In this study, source-specific cancer risk characterization of ambient PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) was performed in central Tehran. The positive matrix factorization (PMF) model was applied for source apportionment of PAHs in the area from May 2012 through May 2013. The PMF runs were carried out using chemically analyzed PAHs mass concentrations. Five factors were identified as the major sources of airborne PAHs in central Tehran, including petrogenic sources and petroleum residue, natural gas and biomass burning, industrial emissions, diesel exhaust emissions, and gasoline exhaust emissions, with approximately similar contributions of around 20% to total PAHs concentration from each factor. Results of the PMF source apportionment (i.e., PAHs factor profiles and contributions) were then used to calculate the source-specific lung cancer risks for outdoor and lifetime exposure, using the benzo[α]pyrene (BaP) equivalent method. Our risk assessment analysis indicated that the lung cancer risk associated with each specific source is within the range of 10−6–10−5, posing cancer risks exceeding the United States Environmental Protection Agency's (USEPA) guideline safety values (10−6). Furthermore, the epidemiological lung cancer risk for lifetime exposure to total ambient PAHs was found to be (2.8 ± 0.78) × 10−5. Diesel exhaust and industrial emissions were the two sources with major contributions to the overall cancer risk, contributing respectively to 39% and 27% of the total risk associated with exposure to ambient PAHs. Results from this study provide an estimate of the cancer risk caused by exposure to ambient PAHs in highly crowded areas in central Tehran, and can be used as a guide for the adoption of effective air quality policies in order to reduce the human exposure to these harmful organic species.

Foam Suppression by Acoustic Means in the Slow Coking of Petroleum Waste

An acoustic method is proposed for foam suppression in the slow coking of petroleum residues. In this approach, pulsed gas motion and a high-intensity acoustic field are created at the point of foam formation. That does not compromise the sterility of the final product. The theoretical principles for formation of an acoustic field whose parameters are in resonance with the acoustic characteristics of the foam are outlined. Laboratory tests of foam suppression on a cold model show that forced disintegration of foam is possible in an acoustic field of intensity up to 120 dB. Experiments on a hot model of the slow coking of petroleum residues indicate the feasibility of foam disintegration without direct contact.

Spatiotemporal variability of hydrocarbons in surface sediments from an intensively human-impacted Xiaoqing River-Laizhou Bay system in the eastern China: Occurrence, compositional profile and source apportionment

Hydrocarbons in coastal sediments record organic matter sources, and thus are widely used to elucidate both natural and anthropogenic inputs and for the estimation of pollution levels. Surface sediments were taken from Xiaoqing River and Laizhou Bay of eastern China in spring and summer of 2014, and were analyzed to determine the characteristics of aliphatic and aromatic hydrocarbons. Various hydrocarbons were identified, including n-alkanes, monomethylated alkanes (MMAs), isoprenoid alkanes, linear alkylbenzenes (LABs), hopanes, steranes and polycyclic aromatic hydrocarbons (PAHs). They were used to track both biogenic (terrestrial plant and microbial inputs) and anthropogenic inputs (petroleum and fossil fuel or biomass burning) in this ecosystem. The major part of hydrocarbons identified came from anthropogenic inputs including petroleum residues and synthetic detergents related hydrocarbons (16.2–90.3%), followed by higher plant (4.5–80.5%) and microbial inputs (0.8–57.5%). Interestingly, significant differences in hydrocarbon concentrations and distributions were observed between spring and summer. In particular, significant higher percentages of microbially derived hydrocarbons, but lower percentages of anthropogenic and vascular plant derived hydrocarbons were observed in summer than spring. Further principal component analyses suggested that the overall distribution of aliphatic hydrocarbons was mainly controlled by seasonality instead of spatiality. In contrast, the distribution of PAHs showed insignificant spatial and seasonal differences. Physical processes such as atmospheric transportation and further deposition, may be factors influencing the distribution of PAHs in the study area with widely biomass and fossil fuel burning. The decoupled distributions of aliphatic and aromatic hydrocarbons warrant further study for a comprehensive understanding of long term sedimentary hydrocarbon sources and input dynamics with increasing human activities. Major findingSeasonal difference in aliphatic hydrocarbon composition was observed in surface sediments of Laizhou Bay, which is mainly caused by stronger phytoplankton and microbial inputs in summer under the overall high pollution background.

A study of the 46-year-old Arrow oil spill: Persistence of oil residues and variability in oil contamination along Chedabucto Bay, Nova Scotia, Canada

Abstract The occurrence, spatial distribution and source of petroleum-related hydrocarbons, and the degree of weathering of Arrow oil residues persisting on the shoreline of Chedabucto Bay, Nova Scotia, were assessed. The hydrocarbons assessed included total petroleum hydrocarbons (TPH), n-alkanes from n-C9 to n-C40, petroleum biomarkers like terpanes, hopanes and steranes, non-alkylated polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues (APAHs). Trapped Arrow oil in the sunken tanker has not experienced any marked weathering. The collected environmental samples could be classified into three groups. Group 1 samples were oil free identified by low TPH, highly resolved fractions, a predominantly biogenic source of n-alkanes, and trace amounts of petroleum biomarkers probably from the historical (1970) oil spill. Group 2 samples had higher TPH and the other targets than Group 1 samples. The mixed petrogenic and terrestrial plant inputs were the source of n-alkanes, while the pattern of APAHs indicated that their source varied from site to site, being either recently released petroleum or Arrow oil residues. Group 3 samples mainly contained oil residues from Arrow oil spill, having very high levels of TPH, APAHs and biomarkers; however, most samples were free of n-alkanes. Group 3 samples were mostly found on the southern shoreline of Chedabucto Bay, especially in the upper to middle intertidal zone of the shorelines characterized by mixed pebble/cobble/boulders. The extent of weathering of n-alkanes and APAHs showed no relation to each other, although n-alkanes were depleted more fully than APAHs for most of the oil residues. Thus, various natural attenuation processes, especially for microbial degradation, have contributed to the aging of these oil residues. The degree of weathering varied with different environmental conditions.