Aquathermolysis of heavy oil in reservoir conditions with the use of oil-soluble catalysts: part I – changes in composition of saturated hydrocarbons

Abstract

This paper is devoted to the study of aquathermolysis processes of heavy oil produced by CSS technology on Boca de Jaruco oil field. Various catalysts based on cobalt, nickel, iron and copper were used for intensification of in-situ upgrading processes of heavy oil. The first paper in series is presented results of transformation of crude oil and its saturate fraction after thermal treatment with and without catalysts by SARA analysis, MALDI mass-spectrometry, FTIR-spectroscopy and gas chromatography. It is revealed, that catalysts provide more deep conversion of asphaltenes and resins into lighter hydrocarbons. Particularly, for the given heavy oil, catalysts based on iron and nickel organic salts are more effective to reduce the content of high molecular weight components (asphaltenes). Saturates fraction after thermal treatment in presence of the catalysts is enriched with lighter alkanes in comparison to the crude oil treated without catalysts. Obtained results show that crude oil recovered by catalytic aquathermolysis processes will be better quality than the original oil in the place.     

Aquathermolysis of heavy oil in reservoir conditions with the use of oil-soluble catalysts: part III – changes in composition resins and asphaltenes

Abstract

This paper discusses aquathermolysis process of heavy crude oil from Boca de Jaruco reservoir, which is developed by CSS method. The catalysts based on cobalt, nickel, iron and cupper are used to intensify the in-situ conversion processes. The active form of catalysts generates after steam injection. The third part of paper discusses conversion of resins and asphaltenes. The influence of thermo-catalytic conditions and composition of catalysts are also studied. The destruction of resins and asphaltenes are observed after thermocatalytic treatments. The changes in composition of resins and asphaltenes are revealed by IR-spectroscopy data.     

The use of a tartaric–Co(II) complex in the catalytic aquathermolysis of heavy oil

A tartaric–Co(II) complex was synthesized and then used in aquathermolysis of heavy oil as a catalyst at relatively low temperature, 180°C. The effects of water amount and catalyst concentration on aquathermolysis were investigated in this work. The crude oil before and after aquathermolysis was fully characterized, and the mechanism of viscosity reduction was discussed at last. The results show that heavy oil can undergo aquathermolysis in the present of water and the tartaric–Co(II) complex at low temperature. Besides, the catalytic aquathermolysis could not only decrease the viscosity of heavy oil, but also remove some heteroatoms, finally making the flow properties better and the quality upgraded.     

Road bitumen's based on the vacuum residue of heavy oil and natural asphaltite: Part I – chemical composition

This work is devoted to studying the possibility of producing bitumen for road construction by using vacuum residue >420°C of heavy oil of the Ashal'chinskoe field in and natural asphaltite Spiridonovskoe field from Permian deposits in Tatarstan. The effect of natural asphaltite as a solid disperse phase element on the structural and group composition of the residual heavy oil product and its malacometrical qualities (penetration, extensibility, softening point, resistance to aging and adhesion) is revealed. The production of samples of compounded bitumen production was carried out by introducing the required amount of the shredded asphaltite to deasphaltizat vacuum residue of heavy oil and heating their mixture to 220°С with vigorous stirring. Changes in the composition and physical and chemical properties of deasphalting the residual heavy oil product, associated with the amount of injected asphaltite, showed the possibility of production of modified bitumen with better adhesion properties that correspond to road bitumen.     

Road bitumen's based on the vacuum residue of heavy oil and natural asphaltite: Part II – physical and mechanical properties

This work is devoted to studying the possibility of producing bitumen for road construction by using vacuum residue >420°C of heavy oil of the Ashal'chinskoe field in and natural asphaltite Spiridonovskoe field from Permian deposits in Tatarstan. The effect of natural asphaltite as a solid disperse phase element on the structural and group composition of the residual heavy oil product and its malacometrical qualities (penetration, extensibility, softening point, resistance to aging and adhesion) are revealed. Samples, compounded bitumen production, were carried out by introducing the required amount of the shredded asphaltite to deasphaltizat vacuum residue of heavy oil and heating their mixture to 220°С with vigorous stirring. Changes in the composition and physical and chemical properties of deasphalting the residual heavy oil product, associated with the amount of injected asphaltite, showed the possibility of production of modified bitumen with better adhesion properties that correspond to road bitumen.     

Nickel–molybdenum sulfide naphthalene hydrogenation catalysts synthesized by the in situ decomposition of oil-soluble precursors

Nickel–molybdenum sulfide catalysts for the hydrogenation of aromatic hydrocarbons have been prepared by the in situ decomposition of oil-soluble precursors Mo(CO)₆ and Ni(С₇H₁₅СOO)₂ in a hydrocarbon feedstock and characterized by HRTEM and XPS. The resulting Ni–Mo sulfide material exhibits high catalytic activity in the naphthalene hydrogenation reaction. An optimum Mo/Ni ratio of 1/2 has been selected.     

The changes of hydrocarbon generation and potential in source rocks under semi-closed conditions with 50–840 bar water pressure

In order to investigate the effects of water pressure on hydrocarbon yields and potential in source rocks, carbonaceous mudstone from drilling in Liaohe Basin was pyrolyzed in simulation with constant water pressure and high-water-pressure experiments. Results demonstrate that the times of expelling hydrocarbon remarkably promote source rocks yielding liquid hydrocarbons. Increasing water pressure may increase the reaction of generating bitumen and oil, and enhance liquid hydrocarbons generation. Results of TOC, Rock-Eval, and elemental analysis in this study suggest that carbonaceous mudstone dominated by type-III kerogen remains a large number of hydrocarbon-generating potential, which may indicate that carbonaceous mudstone has a good potential to yield deep oil and natural gas. Besides, vitrinite reflectance may be the most suitable parameter to describe the maturity of source rocks.     

Crude oil and condensate in the Ordovician–Silurian formations of the Eastern European: The Western Black Sea Basin

The Lower Paleozoic sediments of Eastern Europe extend from Poland to the Black Sea Coasts. The Lower Ordovician Bakacak Formation and Middle Ordovician–Silurian Karadere, Ketencikdere, and F?nd?kl? formations of the Western Black Sea Basin contain mudstones and black shales with sandstone and limestone intervals. The mudstones of the Lower Ordovician do not display any potential. But some intervals of the Middle Ordovician–Silurian black shales have potential for unconventional exploration because total organic carbon (TOC) of organic matter contents ranges from 0.11% to 1.94%. Hydrogen index (HI) values of the Karadere, Ketencikdere, and F?nd?kl? formations are ranging 0–139 mg oil/g TOC. Vitrinite reflection equivalent (Roe) estimation from HI shows that the shales locate within the oil, wet gas-condensate, and dry gas zone. In-situ oil and condensate volumes of the black shales have been calculated between 0 and 2812 mg HC/g TOC. These volumes indicate presence of potentially producible hydrocarbon in the some intervals of the Middle Ordovician–Silurian shales. Mineralogical properties of the Karadere, Ketencikdere, and F?nd?kl? formations are suitable for hydraulic fracturing because the shales are dominated by quartz/carbonate. Quartz ratio ranges from 12% to 91% with an average 53%. Total calcite/dolomite content is an average of 13/0.5%. Total clay mineral chance between 0% and 39% with an average of 21%.