High-sulfur Crude Oil Research Articles

Experimental investigation of mass loss rate and spatial temperature distribution of the pool fire in tunnel

Tunnel fires are accompanied by high temperatures that severely threaten the tunnel stability and the personnel safety, but the burning rate of liquid fuel and spatial temperature distribution near the pool fire had been little studied in a full-scale tunnel. To address this issue, a series of pool fire tests were conducted in a reduced-scale tunnel and a full-scale tunnel, respectively, to investigate the mass burning rate of liquid fuel, temperature variations of the tunnel ceiling and the vertical temperature distribution around the fire source. The results show that the burning of heavy naphtha has a greater damaging effect on the tunnel construction compared to sweet crude oil and high sulfur crude oil. Furthermore, an unified correlation was proposed to describe the fuel mass loss rate in the tunnel. The results obtained in this work would provide a reference for the prevention and rescue of tunnel fires.

A Global Characterization of Sulfur Compounds in a High-Sulfur Crude Oil

A Global Characterization of Sulfur Compounds in a High-Sulfur Crude Oil

Pyrolysis Characteristics and Kinetics Analysis of Oil Sludge with CaO Additive

In the process of exploitation, transportation and refining of high-sulfur crude oil, a large number of oil sludge (OS) with high sulfur content is produced. Pyrolysis has been proved to be an effective method for OS disposal, but for solid waste with high sulfur content, lots of sulfur-containing gases will be released during thermal disposal. The addition of calcium oxide [1] in pyrolysis process is an economical and effective way to capture sulfur-containing gases. In order to understand the pyrolysis process of OS with CaO, a thermogravimetric analyzer was used to conduct pyrolysis experiments of OS with different Ca/S molar ratios (0, 1, 2, and 3) at different heating rates (10, 20, 30 and 40 °C/min). The results showed that with the increase of CaO addition the derivative thermogravimetric curves (DTG curves) showed a gentle trend. In addition, new weight loss peaks were occurred at 700∼900°C and after 1100°C, which were the decomposition of calcium carbonate and calcium sulfate, respectively. The kinetic parameters were solved by Friedman, FWO, and Starink methods, and the results were similar, with an average activation energies (E) value of 214 kJ/mol. The change trend of the activation energy followed by an increase and then a decrease corresponding to the change of energy demand for the reaction. The calculated average values of ΔH, ΔG and ΔS were about 207 kJ/mol, 447 kJ/mol and -0.3250 kJ/mol respectively. When the conversion rate was 0.5, the thermodynamic parameters reached their maximum values.

Comparison of Moving-Bed Catalytic Tar Hydrocracking Processes

In recent years, there has been a trend in the global oil industry to improve the proportion of heavy high-sulfur crude oils in the total volume of extracted and processed resources, reserves of which are estimated at over 800 billion metric tons. Therefore, the main line of oil refining is processing of heavy crudes and residua to allow maximum use of the hydrocarbon potential and yield of high-margin products. Hydrogenation processes of heavy raw materials are most attractive in terms of product quality. This article analyzes tar hydrocracking processes that are either in operation or at the stage of full-scale testing. These include Veba Combi-Cracker (VCC), Uniflex, suspended-bed catalyst hydrocracking (ENI), and vacuum residue hydroconversion (TIPS RAS). These technologies use heterogeneous catalysts and are designed to obtain the largest possible amount of liquid products. This article discusses the features of each technology, highlights their advantages and disadvantages, shows the main approaches to process management, and speculates about the development of these technologies. Tar refining is a major process in heavy oil upgrading, and the development of efficient tar-processing methods will influence refinery configurations and management.

Geochemical characteristics and genesis of crude oils with complex physical properties in the eastern part of the southern gentle slope of Dongying Sag

The crude oil in the eastern part of the southern gentle slope of Dongying Sag has complex physical properties, and various crude oils with different properties such as heavy oil, high sulfur oil, and high wax oil have developed. The complexity of the physical properties reflects the influence of the source rock properties, crude oil migration process, and secondary alteration after accumulation on crude oil characteristics. Through systematic analysis of geochemical data, the formation mechanism of crude oil with these special physical properties has been clarified. The result of hydrocarbon generation at an early stage from source rocks rich in high-sulfur kerogen deposited in a euxinic waterbody is the cause of high-sulfur crude oil with low maturity in Wangjiagang oil field. While the shallow reservoir burial depth and the resulting biodegradation is the mechanism of the formation of high-sulfur crude oil in Le’an oil field with higher maturity. Biodegradation is the main mechanism of the formation of heavy oil, and the recharge of hydrocarbons into the degraded crude oil reservoirs leads to the complication of crude oil density. Both the hydrocarbon generation of organic matter rich in terrestrial higher plants and phase-controlled fractionation during hydrocarbon migration lead to the generation of high wax crude oil.

Study on the Migration Characteristics of Sulfur and Nitrogen during Combustion of Oil Sludge with CaO Additive

Oil sludge (OS) is a typical hazardous waste from the petrochemical industry. Currently, the increasing ratio of high-sulfur crude oil worldwide that results in the growth production of OS with high sulfur content has drawn much attention. OS incineration with calcium-based additives has great potential to be an efficient and clean approach for the large-scale treatment of high-sulfur-containing OS. In this work, the migration characteristics of sulfur and nitrogen during OS combustion with CaO additives were investigated by an online thermogravimetric-mass spectroscopy-Fourier transform infrared (TG-MS-FTIR) spectroscopy system and a fluidized combustion reactor system, respectively. Results indicated that CaO significantly reduced the emissions of SO2 and NOx during fluidized combustion of OS, and the minerals in OS and CO2 in the flue gas affected the utilization efficiency of CaO additive. The sulfur fixation capacity by CaO decreased with the increase of combustion temperature and almost completely failed at 1100 °C. The capacity of CaO to reduce NOx emission increased first followed by a decrease with the increase of combustion temperature. Furthermore, CaO significantly promoted the conversion of HCN to other nitrogen-containing gases, which can promote the production of NO by the precursors (HCN and NH3) and the reduction reaction of NO to N2. To the best of our knowledge, there is still not an efficient and clean technology for large-scale treatment of OS in China. This study is helpful for the massive utilization of high-sulfur-containing OS.

Removal of Hg2+ from flue gas by petroleum thioether

Petroleum thioether showed excellent flue gas de-Hg2+ ability to control mercury reemission. Petroleum thioether was prepared with high-sulfur crude oil as raw materials and characterized by FT-IR. The thioether group content was 0.104 g/g by the potentiometric titration with lead acetate as titrant. The Hg2+ removal performance of petroleum thioether was studied in simulated flue gas. The experiment results exhibited that petroleum thioether showed excellent Hg2+ removal efficiency in flue gas without threat of mercury reemission, and the process for Hg2+ capture by petroleum thioether was exothermic and went on smoothly below 60°C. 6 M HCl could be used to regenerate petroleum thioether trapped Hg2+, and there acquired a regeneration of 89.6%, which meant this Hg2+ removal treat showed low operation cost. Moreover, the regeneration of petroleum thioether captured Hg2+ facilitated the centralized processing of mercury and prepared well for the full utilization of mercury resources.

Isolation and characterization of sulfur compounds in a lacustrine crude oil

A high-sulfur (4.69 wt%) crude oil was discovered in the China Bohai Bay Basin which is known to contain low sulfur crude oil. The composition of this high sulfur crude oil and its geological origin are unknown. In this study, thiophenic and sulfidic sulfur compounds were isolated from the crude oil by methylation/demethylation and characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and gas chromatography-mass spectrometry (GC–MS). Relatively high abundance of sulfur compounds with 30 carbon atoms and 5–7 double bond equivalence (DBE), which were assigned to sulfurated steranes with thiophene or tetrahydrothiophene moieties. Some of these compounds have not been reported in fossil fuels. In addition to commonly found sulfur compounds in petroleum feedstock, such as benzothiophenes and dibenzothiophenes, other structural sulfur compound types were detected: long-chain 2,5-di-n-alkylthiolanes, 2,5-di-n-alkylthianes, bicyclic terpenoid sulfides, isoprenoid thiophenes, and isoprenoid benzothiophenes. The presence of abundant biomarker sulfur compounds suggests that the sulfuration of the high sulfur crude oil was occurred in the early diagenesis stage instead of a thermochemical sulphate reduction (TSR) process.

Kinetics of sulfur removal in high shear mixing-assisted oxidative-adsorptive desulfurization of diesel

Abstract Current global environmental regulations require deep desulfurization of prevailing high-sulfur crude oil reserves to limit toxic sulfur oxide emissions during fuel combustion. In this study, deep desulfurization of diesel was carried out in two sequential batch steps: (1) oxidation of refractory sulfur compounds in diesel into sulfones and (2) adsorption of the polar sulfur-species in the resulting organic phase onto commercially available adsorbents. Oxidative desulfurization of diesel was performed in a glass vessel equipped with a high shear mixer set at 12,000 rpm. Phosphotungstic acid, tetraoctylammonium bromide and hydrogen peroxide were used as catalyst, phase transfer agent and oxidant, respectively. Adsorptive desulfurization, on the other hand, was carried out using powdered alumina, granular alumina, powdered activated carbon (PAC), and granular activated carbon (GAC) adsorbents. Characterization results showed that powdered alumina and PAC appear to be aggregates of small crystalline structures, with PAC having larger surface area of 846 m2 g−1 compared to powdered alumina at 129 m2 g−1. Micropores were detected in PAC, while the porosity of powdered alumina was attributed to the presence of mesopores. Sulfur removal by the four types of adsorbents conformed to the pseudo-second order model, implying that chemisorption was the rate-limiting step. The computed adsorption capacities from the kinetic model at 3.47, 1.09, 3 and 1.09 mg g−1 were in agreement with the experimental adsorption capacities at equilibrium of 3.36, 0.98, 3 and 1 mg g−1 for powdered alumina, granular alumina, PAC and GAC, respectively. The 2-line Weber-Morris plots of the four adsorbents indicated the effects of boundary layer diffusion and intraparticle diffusion in sulfur removal. The values of kid1 and kid2, as well as I1 and I2, implied that boundary layer diffusion proceeded at a faster rate than the rate-determining step which was intraparticle diffusion. Higher intraparticle diffusion coefficient values were observed for powdered alumina due to its larger particle size and, consequently, smaller surface area where the sulfur compounds tend to be more readily adsorbed.

耐硫加氢催化剂研究进展

催化加氢是常见的化工生产工艺，具有绿色高效等特点。但是，对于含硫化合物的催化加氢过程，易发生催化剂硫中毒的问题。而随着劣质高含硫原油产量的进一步增加，以及工业上对一些有机硫化合物诸如苯并噻吩类化合物的加氢还原产物的迫切需要，寻找合适的耐硫加氢催化剂成为了人们关心的热点问题。本文首先阐述了不同的硫化物(包括硫化氢、硫酸盐与有机硫)使催化剂中毒的机理，然后根据催化剂的失活机理分类阐述了各种不同的耐硫加氢催化剂的最新进展，并对目前的耐硫加氢催化剂进行了分析与展望。 Catalytic hydrogenation is a common chemical production process, which is with green and effi-cient features. However, the catalysts are prone to be sulfur-poisoning in the process of catalytic hydrogenation with sulfur-containing compounds. With the further increase in the yield of poor high-sulfur crude oil, as well as the urgent need in the industry for some hydrogenation products of organic sulfur compounds such as benzothiophenes, finding suitable sulfur-resistant hydrogenation catalysts has become a hot topic of concern. Firstly, the mechanism of poisoning of catalysts with different sulfides (including hydrogen sulfide, sulfate and organic sulfur) were described in this paper. Then, according to the deactivation mechanism of the catalyst, the latest progresses of various sulfur-resistant hydrogenation catalysts were discussed. At last, the current sulfur-resis- tant hydrogenation catalysts were analyzed and forecasted.

Separation and Research of Organosulfur Compounds Content of High-Sulfur Crude Oil

Separation and Research of Organosulfur Compounds Content of High-Sulfur Crude Oil

Molecular Transformation of Crude Oil in Confined Pyrolysis System and Its Impact on Migration and Maturity Geochemical Parameters

The compositions of crude oils can vary significantly during thermal maturation through cracking and aromatization. In this study, an immature high sulfur crude oil was pyrolyzed in a closed gold-tube system with heating rates of 20 °C/h and 2 °C/h, respectively, to simulate the thermal maturation process of crude oil. The molecular compositions of heteroatom-containing compounds in crude oil were investigated by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) while the impact of thermal maturation on migration and maturity geochemical parameters were investigated by gas chromatography–mass spectrometry (GC-MS). Based on the analysis of pyrolysis products, the compositional variations of heteroatom-containing aromatic compounds and the validity of the aromatic geochemical parameters during thermal maturation were investigated. When the equivalent vitrinite reflectance value (Easy %Ro) was greater than ca. 0.85, alkyl chain cracking was the major reaction and led to the producing of...

Study on the Desulfurization of High-Sulfur Crude Oil by the Electrochemical Method

The SnSb intermetallic compound was synthesized by chemical precipitation with NaBH4 as a reducer, and then it was applied in the electrodesulfurization of Saudi crude oil as functional desulfurization material. The prepared SnSb intermetallic compound was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). Additionally, the raw material and treated oil were analyzed through gas chromatography–pulsed flame photometric detector (GC–PFPD) and gas chromatography–mass spectrometry (GC–MS). The results showed that the SnSb intermetallic compound was restored with NaBH4 with a larger particle size, lower surface area, lower crystallinity, and “brick-shaped” structure. The desulfurization efficiency for sulfocompounds with a small molecular weight is higher. It should be especially noted that benzonaphthothiophene was hardly removed by traditional hydrogenation desulfurization, whereas it could be subtracted partly via electrochemical adsorption...

Burning sulfur crude oil in a fluidized catalyst bed

The possibility of the environmentally friendly burning of sulfur crude oil in a fluidized catalyst bed is studied in order to use this method in an energy plant for local heat supply. Two types of oil are used in the experiments: sulfur and high-sulfur crude oil. The oils are combusted in a bed of aluminum–copper–chrome catalyst for the deep oxidation of organic compounds, and in a bed of inert material for comparison. The efficiency of sulfur crude oil combustion depends on the amount of toxic products in the combustion gas (CO, SO2 and NO x ) and how complete the burning-out of organic components is. Calcite is used in a fluidized bed to remove SO2 from flue gas. The burning of sulfur crude oil in a fluidized catalyst bed with calcite is shown to result in complete burning-out at relatively low temperatures (700°C) and excludes the presence of CO and SO2 in the combustion gas. At the same time, the concentration of nitrogen oxides remains minimal and does not exceed environmental norms.

Affection of High Sulfur and Naphthenic Acid Crude Oil Acted on Refinery Equipment

Introduced the characters of crude oils containing sulfur and naphthenic acid, analyzed the corrosion and safety of this kind of oil acted on refinery equipment, investigated the corrosion on oil atmospheric and vacuum distillation equipment, delayed coking unit and gas desulphurization unit. Tabled a proposal to forecast life of the device using risk based inspection and grey system theory, assured the equipment to run long-term and safety.

Sulfur compounds in crude oils of the Jurassic-Paleozoic play in Western Siberia

The composition and structure of sulfur compounds in low-, medium-, and high-sulfur crude oils from the Jurassic-Paleozoic play of Western Siberia have been studied. It has been shown that the distribution of organic sulfur compounds in the oils is determined by the depositional environment of source organic matter. Highly alkylated dibenzothiophenes (up to 15 carbon atoms in the aliphatic chain), naphthobenzothiophene isomers and their C1 and C2 homologues, and the α-n-alkylthiolane and α-n-alkylthiane homologous series have been identified for the first time among sulfur compounds of Western Siberia crude oils.

Balancing Response Operations with Safety, the Environment and Commerce

ABSTRACT On January 23, 2010, a double hull tank vessel spilled nearly 9,500 barrels of high sulfur crude oil into the Sabine-Neches River (SBR) in Port Arthur, Texas. An ensuing evacuation of surrounding areas, coupled with the potential environmental impact and closure of the Intracoastal Waterway, elevated public, political and environmental concerns. Through an effective multi-agency Incident Command, rapid call up of abundant response resources to properly implement pre-identified response protocols, and the development of innovative response tactics, response managers successfully balanced environmental, commercial and safety concerns to execute a highly effective spill response in one of the busiest shipping thoroughfares in the United States. Collectively, the support of a cohesive Unified Command to execute operational strategies, and the RP's diligence in ensuring all needed response resources were quickly made available, enabled the command post to be stood down and the majority of the cleanup ...

Experimental Research on Environmental Friendly Ash Aerated Concrete

Aerated concrete is kind of normal silicate products, which is made by hydration of lime, cement, gypsum fly ash/sand, forming agent. And it has become the major wall material of frame structure caused by its characteristics of light weigh, high strength, and heat insulation. Petroleum coke is the by-product of delayed coking system in oil refinery. Oil refinery in coast area of east China mainly exploits high-sulfur crude oil from Middle East. The petroleum coke contains even 5-8% sulphur, and calcium injection desulphurization is usually employed to reduce the SO2 emission, and leads to that Ca/S of reaction is up to 2.0-2.5. Therefore, there remain many unhydrated Lime and desulfurized gypsum in petroleum coke. It presents drying powdery and a favorable cementing performance. In this paper, chemical and mineral compositions of petroleum coke desulfuration residue are analyzed by means of X-ray fluorescence spectrometer and X-ray diffracto-meter. And lime and gypsum are replaced by petroleum coke desulfuration residue to produce aerated concrete. The experimental results indicate that products made of high-sulfur petroleum coke desulfuration residue and fly ash has better performance than traditional lime aerated concrete products. The fly ash-desulfuration residue aerated concrete products possesses the dry density level of B06 [1] and strength of 4.5MPa. Consequently, it should have expansive application potential because of their prominent economic, social, and environmental benefits.

Separation of rare metals in plasma chemical pyrolysis of petroleum residues

A method is proposed for separating industrial carbon with rare metals from pyrolysis gases obtained in plasma-chemical processing of hydropyrolysis residues from high-viscosity high-sulfur crude oil (HHC).

Mild catalytic hydropyrolysis of high-viscosity, high-sulfur crude oil

The possibility of increasing the light cut content during mild catalytic hydropyrolysis of high— viscosity, high—sulfur crude oil was investigated. The new technology allows attaining a greater than 60 wt. % yield of motor fuels due to decomposition of resins and asphaltenes without expensive catalysts. The <350°C cut obtained can be used without hydrotreating for synthesis of environmentally safe motor fuels.