High-sulfur Oil Research Articles

Burning of Sulfur-Containing Liquid Fuels in Fluidized Catalyst Bed

Results are presented of the process of burning of sulfur-containing liquid fuels in a nonisothermal fluidized bed of a ShchKZ-1 industrial catalyst for the example of sulfurous and heavy high-sulfur oil. The optimal (“dropdown”) temperature profile in the bed was determined. This profile is characterized by a downstream decrease in temperature from 700 to 500°C. A mathematical simulation based on the description of experimental data on the variation of the sulfur concentration at the exit from the adsorbent (calcite) bed at its varied charge was used to calculate the specific capacity of the sorbent to be (14.2-15.9) x 103 g cm3. It was shown that the potential capacity of calcite in fluidized bed exceeds by an order magnitude that in a fixed bed.

Kinetics of elemental sulfur reduction by petroleum hydrocarbons and the implications for hydrocarbon thermal chemical alteration

Abstract Although sulfur-containing compounds are known to play a significant role in the diagenic and catagenic processes that generate oil and gas, relatively little is known about the kinetics of reactions between elemental S and petroleum hydrocarbons. To investigate this subject, a series of closed-system pyrolysis experiments using paraffin, a low-sulfur oil, and a high-sulfur oil with and without elemental S were conducted, and first-order chemical kinetics were fit to the experimental results. The average value for the activation energy required to reduce elemental S to H2S and to thermochemically alter higher molecular weight hydrocarbons to methane was calculated to be 193 kJ mol−1 (46 kcal mol−1). The results of this study demonstrate that under typical geologic conditions the rate of reduction of elemental S to H2S by petroleum hydrocarbons is quite rapid. The maximum time for substantial amounts of elemental S to persist in contact with petroleum hydrocarbons is estimated to be no more than a few million years in cool reservoirs (e.g., 120 °C) the half-life of elemental S may be as short as hundreds of years. Additionally, the presence of elemental S substantially lowers the onset temperature of hydrocarbon thermal chemical alteration (TCA). The activation energy for TCA of a low-sulfur oil to generate methane is estimated to be lowered by 92 kJ mol−1 (22 kcal mol−1) due to the presence of elemental sulfur. Consequently, the presence of elemental S in petroleum reservoirs is expected to lower the thermal stability of oil and decrease the maximum depth at which oil occurs within a basin (thermal deadline). The observed acceleration of hydrocarbon TCA is possibly due to organic sulfur compounds (e.g., thiols and sulfides) that form through the reaction of H2S or polysulfides with hydrocarbons and subsequently thermally degrade leading to the formation of sulfur radicals that in turn enhance TCA reactions.

Pyrolysis analyses and bulk kinetic models of the Late Cretaceous oil shales in Jordan and their implications for early mature sulphur-rich oil generation potential

In this study, oil shale samples were collected from Late Cretaceous Muwaqaar Chalk Marl Formation (MCM) in Jordan to study their petrologic and organic geochemical properties. Pyrolysis and bulk kinetic techniques were performed on the Late Cretaceous oil shales. The results of this study were used to characterize the different organofacie types in the Late Cretaceous oil shales and their effect on the petroleum type generated during thermal maturation and the temperature of petroleum generation. On the basis of the geochemical results, the analysed Late Cretaceous oil shales contain predominantly Type II and rarely Type I kerogens.These kerogens are consistent with the high dominate of sapropel organic matter (i.e., alginite and amorphous organic matter). A good correlation is noted between increasing abundance of organic matter and the kerogen type that was derived from an open pyrolysis–gas chromatography (Py–GC). The Py–GC data indicate the analysed oil shale samples contain heterogeneous organic matter of the kerogen Type II-S. It is interesting to know that this sulphur-rich kerogen (Type II-S) can generate high sulphur oils at low maturity ranges. This is consistent with the predicted temperature petroleum generation from bulk kinetic models. The bulk kinetic models in this study indicate that the main phase of petroleum formation from the thermally immature Late Cretaceous oil shales occur between 122 and 148 °C. These temperature values of the petroleum generation are generally consistent with the kerogen type II-S and further indicate that the analysed oil shale samples can generate sulfur-rich oils at early stage of kerogen cracking.

Influence of Temperature on the Hydrogenation of Oil Shale from the Kashpir Deposit

The effect of the hydrogenation temperature of oil shale from the Kashpir deposit on the yield and the properties of the resulting liquid hydrocarbons and gasoline and diesel fractions separated from them was studied. It was found that synthetic oil can be obtained from high-sulfur oil shale with the use of hydrogenation processing. In this case, it is possible to extract more than 90% of the organic matter of oil shale. Depending on the temperature of this processing, the sulfur content of the synthetic oil varied from 2.8 to 4.2 wt %, and the nitrogen and light fraction contents varied from 1.3 to 1.6 and from 34 to 67 wt %, respectively.

Hydroconversion of Oil Shale on Natural Mineral Matrices

The hydroconversion of high-sulfur oil shale in the presence of natural mineral matrices: shale ash, sandstone, and clay has been investigated. It has been shown that mineral matrices containing clays and iron exhibit catalytic activity during the hydroconversion of oil shales. Due to this activity, a significant reduction in the sulfur and nitrogen content and an increase in the amount of light fractions in the resulting synthetic oil are achieved.

Composition of Products of Transformation of High-Sulfur Oil Shale in Supercritical Benzene

The conversion of high-sulfur oil shale in a flow of supercritical benzene under pressure of 10 MPa and temperatures up to 400°C is studied. The composition of the formed liquid products is characterized by the methods of IR- and 1H NMR-spectroscopy, structural group analysis, and chromato-mass spectrometry. It is shown that the content of resin and asphaltene compounds in the pyrolyzates decreases with the increase of temperature and the fraction of aromatic fragments in their composition increases, while the fraction of aliphatic fragments decreases. The amount of polar components decreases in the oily fraction. The compounds identified in the oils are represented by normal and branched alkanes; alkenes; saturated and unsaturated naphthenes; and mono-, bi-, tri-, tetra-, and pentacyclic aromatic hydrocarbons; as well as compounds of thiophene-, benzo-, dibenzo-, and naphthothiophene series, aliphatic ethers, and ketones.

Characterization of Particle and Gaseous Emissions from Marine Diesel Engines with Different Fuels and Impact of After-Treatment Technology

The International Maritime Organization (IMO) Marine Environment Protection Committee (MEPC) and some countries have gradually strengthened the laws regulating ship exhaust emissions. The aim of this paper is to estimate the impact of an after-treatment technology exhaust gas cleaning (EGC) system on marine diesel engine emissions and the cost advantage compared to using low-sulfur fuel oil. The emission characteristics of SO2 and particulate matter (PM) produced from high sulfur oil and low sulfur oil in a low-speed two-stroke marine diesel engine were also presented. The removal efficiency of SO2 has been tested and the PM removal efficiency was also predicted in this study. When using high sulfur oil, the emission factor of SO2 and PM were from 8.73 g/kWh to 11.6 g/kWh and 2.0 g/kWh to 2.7 g/kWh, respectively. These values are significantly higher than the emission values from using low sulfur oil. The fuel sulfur content (FSC) was the key factor affecting the emission factors of SO2 and PM. The fuel change could reduce the mass emission factor of PM, which is above 90% for the total particle emission with the two fuels. When using the EGC system, the desulfurization efficiencies were above 99%. The pH values at a 25, 39, 53, and 67% load were also stabilized to be around 7.5, 7.6, 7.7, and 8, respectively. The EGC system can also capture part of the primary PM and secondary PM formed from SO2. The EGC system was more effective for PM of the size larger than 1 μm. Thus, according to this study, the usage of low sulfur oil and EGC will also substantially decrease the emission of currently unregulated hazardous chemical species in the exhaust gas of ships in addition to satisfying future emissions regulations of ship. Furthermore, the EGC system also had a significant cost advantage compared to using low-sulfur fuel oil.

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

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

Low-Sulfur Fuel and Oil Production

Problems of transforming heavy crude high-sulfur oil into low-sulfur fuels and oils become increasingly urgent for oil refineries. The main reason for that is depletion of low-sulfur oil-fields and following rise of heavy crude oil share in world's oil production. Desulfurization of oil and petroleum residues is performed by breaking down or extraction of sulfur and sulfur compounds with catalyst and chemical additives which leads to considerable rise in price of refinery. Desulfurization technology proposed in the following research involves simultaneous use of the acoustic and hydrodynamical cavitation for breaking down long molecular connections. Oil refinery was performed in the electromechanical vortex layer activator which intensified mechanoactivation processes by intensive movement of ferromagnetic elements in the external magnetic field.

Pitting Behavior of 304 Stainless Steel in Simulated Condensate in Refining High Sulfur and Salt Heavy Oil

The pitting behavior of 304 stainless steel in the simulated condensate with different salt content (4 mg/L, 8 mg/L, 16 mg/L, 32 mg/L, 64 mg/L) and sulfur content (1.2 g/L, 2.5 g/L, 5 g/L) was studied using potentiodynamic polarization curve and static immersion methods. The simulated condensate was simulating the condensed water in the unit of refining heavy oil with high salt and high sulfur. The results showed that with the increase in chloride ions concentration, the pitting potential of 304 stainless steel decreased and the pitting sensitivity increased. The pitting sensitivity of 304 stainless steel also increased with the increase in sulfide ions concentration. In several experimental mediums, when the concentration of chloride ions and sulfide ions were 64 mg/L, 5 g/L respectively, the number and the size of corrosion pits both were the largest, the pitting behavior was the most serious.

Changes of Microstructure and Properties of G105 Drill Pipe in H<sub>2</sub>S Environment

H2S corrosion has become one of the key factors that has impact seriously on the exploration and development of high-sulfur oil and gas. In order to study the change of microstructure and properties of G105 steel drill pipe in H2S environment, different concentrations of H2S (300ppm, 400ppm, 500ppm, 600ppm) were used respectively at room temperature to make corrosion immersion test on the G105 drill pipe, and then tensile test, impact test, hardness test, metallographic analysis, scanning electron microscopy (SEM) observation and EDS spectrum analysis. The results showed that in the range of H2S concentration provided in tests, pipe materials was corroded quite seriously, microstructure changed obviously, comprehensive mechanical properties decreased significantly, and the range decreased first and then increased and decreased again. The type of fracture is classified as the pore ductile fracture, some of them appear prospective cleavage characteristics, and, fracture place exist severe solute partial clustering phenomenon. In addition, high concentration of Sulfur was found in impact fracture surface. The results would provide a reference for our understanding of the corrosion behavior of the drill pipe materials in H2S environment and the development of new anti-corrosion materials drill pipe.

The effects of magnesium of Zn–Mg–Al additives on catalytic cracking of VGO and in situ reduction of sulfur in gasoline

The scope of the present study is to describe the cracking behavior of hydrocarbons and the reduction of sulfur in gasoline in fluid catalytic cracking (FCC) process using Zn–Mg–Al additives with varying the Mg/Al molar ratios. Experiments have been carried out on a micro-activity-test (MAT) reactor using high-sulfur vacuum gas oil (VGO) feed and zinc impregnated Mg–Al spinels as additive and the commercial cracking catalyst. It was found that Zn–Mg–Al additives exhibited enhanced Lewis acidity compared with the corresponding Zn-free Mg–Al spinels. The MAT results indicated that the addition of additives reduced the yields of liquid petroleum gas and coke at low Mg contents but increased the coke yield at high Mg contents. Overall, the additives improved the yields of gasoline and diesel. It has also been shown that the rich Lewis acidity had a positive effect on the conversion of aromatic sulfur species of gasoline and the maximum reduction of gasoline sulfur was achieved with Zn/Mg4.0Al2O3 due to the synergistic effect of basicity and Lewis acidity.

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.

The physicochemical characteristics and hydrocarbon composition of crude oils of the Timan–Pechora petroliferous basin

The total hydrocarbon composition and average structural-group characteristics of typical Paleozoic crude oils of the Timan–Pechora petroliferous basin are described. The hydrocarbon (HC) types of crudes are compared, which were conventionally determined from the composition of their gasoline fractions, by mass-spectrometric analysis of the HC composition of crudes, and by structural-group analysis of crudes, based on radiospectrometric data. The analyses have shown the presence of 30 structural types of HCs with up to 43 carbon atoms. The whole series of members up to C43 are specific only for HCs with no more than three rings in the molecule. It has been established that the carbonate strata in the basin under investigation, independently of the depth of their occurrence and the age of the host deposits, generate and accumulate heavy high-resin high-sulfur oils rich in alicyclic structures and assigned by HC composition to the naphthene–methane or even naphthene type. Terrigenous reservoirs here abound in crudes of methane–naphthene type. The contents of sulfur and resinous substances and the fraction of carbon atoms in alicyclic HC structures decrease as the depth of occurrence of the host deposits grows, thus reflecting the known gradual process of “methanization” of petroleum composition.

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.

Standard Oil as a Technological Innovator

A century ago, in 1911, the U.S. Supreme Court issued its path-breaking decision in the monopolization case against the Standard Oil Companies. Standard pleaded inter alia that its near-monopoly position was the result of superior innovation, citing in particular the Frasch-Burton process for refining the high-sulfur oil found around Lima, Ohio. This paper examines the role of Hermann Frasch in inventing and developing the desulfurization process, showing that Standard failed to recognize his inventive genius when he was its employee and purchased his rights and services only after he had applied it in his own Canadian company.

Thermodynamic analysis of the gasification product composition of vacuum residuum from the hydroconversion of heavy crude fractions oil

Heavy residual stock obtained by the vacuum distillation of the hydroconversion products (T = 425°C; P = 6 MPa; a nanoheterogeneous catalyst based on molybdenum sulfide) of heavy residual carbonic (high-sulfur) oil is a starting material for gasification. The equilibrium composition of gasification products (P = 0.1 MPa; α = 0.3; 20 wt % H2O) over the temperature range of 519–1626 K was calculated using chemical thermodynamics methods. The yields of the main compounds of Mo, V, Ni, Ag, Au, As, Co, Ga, Fe, Al, Si, Ca, and Mg (mol/kg residue) and their amounts in gas and condensed phases were determined. The volumes and compositions of gaseous products were also determined as functions of temperature at different sulfur concentrations of 9.5 and 4.75 wt % in the starting vacuum residue.

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.

Extractive refining of high-sulfur diesel fraction to remove organic sulfur compounds and aromatic hydrocarbons

Experiments were performed on single-step extraction of organic sulfur compounds and aromatic hydrocarbons from the diesel fraction of high-sulfur oil containing sulfur mainly in the sulfide form with various aprotic and protic selective solvents and with extraction systems polar extractant-hexane.

Ni-Mo-Titania-Alumina Catalysts with USY Zeolite for Low Pressure Hydrodesulfurization and Hydrocracking

Titania-alumina based catalysts were prepared and tested for hydrodesulfurization (HDS) and hydrocracking activity in the temperature range 300°C to 350°C in a fixed-bed reaction system using 4,6-dimethyldibenzothiophene (4,6-DMDBT) dissolved in n-hexadecane. Characterization results show that the metal-loaded titania-alumina possesses a high pore radius and pore volume but low surface area. The physical mixing with USY zeolite increased its surface area. The surface area was further increased upon mixing with nanoporous alumina. The total ammonia based acidity of the titania-alumina was lower than that of the ultra stable Y (USY) zeolite, but Ni-Mo loading was found to increase the acidity. The acidity of titania-alumina was further increased by mixing with nanoporous alumina and USY zeolite. All catalysts exhibited good HDS and hydrocracking activity for 4,6-DMDBT and n-hexadecane. The catalyst showing the highest HDS activity using 4,6-DMDBT was further tested and was found to have reasonable activity for both low- and high-sulfur vacuum gas oil feeds. This study demonstrated low-pressure HDS activity of the catalysts.