The influence of sulfur on the structural-dynamic parameters of petroleum systems studied by the NMR technique

Kashaev, R. S.; Khairullina, I. R.

doi:10.1134/s0965544109060103

Cited by 3 publications

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“…9 High-resolution 1 H and 13 C NMR have been used in the analysis of VR in the past, including different studies about the structural parameters of asphalts, 10 structural changes during asphalt oxidation, 11 chemical transformations during Arab asphalts aging, 12 studies of the amorphous and crystalline phases of asphalts, 13 the percentage of aromatics and aromatic substitution of asphalts, 14 the chemical and rheological properties of modified asphalts, 15 and the characteristics and distribution of the functional groups before and after aging of modified asphalt with crumb rubber (CR) and the addition of styrene−butadiene−styrene (SBS) and sulfur. 16 Low-resolution 1 H NMR has been used to measure the relaxometric properties of crude oils, throughout their T 1 and T 2 relaxation times and their diffusion, which are employed to study some properties and features including porous structures in asphaltic cements, 17 changes in the activation energies of asphalts with different sulfur concentrations, 18 viscosity and asphalts aging, 19 relative viscosity of binder in asphalt concrete without the need for binder extraction, 20 the effect of recycled materials and recycling agents in asphalt blends samples, 21 the effect of modifiers on the bitumen microstructure aging process, 22 the monitoring of the long-term aging of asphalt binder in mixture cores without binder extraction, 23 and the softening point and their response to specific conditions of bitumen which has been doped by different percentages of polyphosphoric acid (PPA). 24 In this paper, a study of the physicochemical, spectroscopic, and relaxometric properties of the VR produced in refinery and those modified into asphalts to fabricate pavements, which were measured weekly, for one year long is reported.…”

Section: Introductionmentioning

confidence: 99%

“…Low-resolution 1 H NMR has been used to measure the relaxometric properties of crude oils, throughout their T 1 and T 2 relaxation times and their diffusion, which are employed to study some properties and features including porous structures in asphaltic cements, changes in the activation energies of asphalts with different sulfur concentrations, viscosity and asphalts aging, relative viscosity of binder in asphalt concrete without the need for binder extraction, the effect of recycled materials and recycling agents in asphalt blends samples, the effect of modifiers on the bitumen microstructure aging process, the monitoring of the long-term aging of asphalt binder in mixture cores without binder extraction, and the softening point and their response to specific conditions of bitumen which has been doped by different percentages of polyphosphoric acid (PPA) …”

Section: Introductionmentioning

confidence: 99%

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Study of Vacuum Residues and Their Transformation to Asphalts for the Pavement Industry by Nuclear Magnetic Resonance and Chemometric Methods

2019

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This paper reports the findings of a one-year long study, that every week measured the physicochemical properties (P: penetration; A: softening; Ip: penetration index; V: rotational viscosity, R: mass loss), and the spectroscopic and the relaxometry properties via nuclear magnetic resonance, of the vacuum residues (VR) produced in a refinery and those modified into asphalts to fabricate pavements with penetration grade 60/70. The evolution of the structural changes, along the time of study, was measured via high-field and low-field 1H NMR and analyzed through multivariate statistical methods. The attained results with high-field 1H NMR showed that when the VR are oxidized, the proportion of protons associated with the high-molecular-weight polyaromatic increases. On the other hand, the low-field 1H NMR results, through a greater number of unimodal distribution plots of T 2 relaxation time, showed the homogenization of the aggregation as well as of the dynamic properties of the molecules, thus indicating that the aging of asphalts cannot be prevented despite the treatment. After analysis of the physicochemical properties, it was found that some refinery VR samples do not meet the quality specifications of penetration grade 60/70, dictated by the National Roads Institute of Colombia (INVIAS), to be employed as raw material in the manufacturing of pavements, but only after being processed and modified.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Study of Vacuum Residues and Their Transformation to Asphalts for the Pavement Industry by Nuclear Magnetic Resonance and Chemometric Methods

2019

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“…NMR relaxometry has such capabilities. The potential of this method was demonstrated using several physical chemical properties of oil, residuals, and asphalts as examples [1,2]. It was also established that component concentrations (asphaltenes and resins) found from NMR relaxometry differed from the component composition determined according to GOST 2177-99 (ISO 3405-88).…”

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confidence: 99%

Effect of irradiation in the visual and infrared spectral regions on nuclear magnetic relaxation parameters of protons in oil products

Kashaev

Gazizov

2010

J Appl Spectrosc

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538.955:538.958 The influence of laser and non-coherent irradiation on the state of oil components has been studied at wavelengths of 630 and 1825 nm, respectively. New results reflecting changes in structural-dynamic parameters of the molecular motion as a function of exposure time have been obtained. The variations of NMR parameters during NIR irradiation of an oil sample prepared with the addition of paraffin (docosane) seem to be connected with "washing out" of these nanodimensional structures and can be explained theoretically in terms of the phenomenological description of the energy-level population behavior. The method of NMR relaxometry used in parallel with laser and non-coherent radiation in the NIR spectral region has been shown to enable one to readily determine oil components that are difficult to estimate by conventional techniques.Introduction. Existing analytical methods (IR spectroscopy, x-ray structure analysis, mass spectrometry) are poorly suited for rapid analysis of nanostructures that affect the quality of fuels and dispersed oil systems because of the need to prepare samples. High-resolution NMR requires a sophisticated instrument and also cannot provide information about high-molecular-weight oil compounds (HMWC) and cannot be used conveniently for analysis. However, analysis and rapid monitoring of HMWC in fuel and crude oil are necessary for optimization of industrial processes, prevention of man-made accidents, and protection of the environment. NMR relaxometry has such capabilities. The potential of this method was demonstrated using several physical chemical properties of oil, residuals, and asphalts as examples [1,2]. It was also established that component concentrations (asphaltenes and resins) found from NMR relaxometry differed from the component composition determined according to GOST 2177-99 (ISO 3405-88). This was due to hindrance of the molecular motion of HMWC structural fragments and shortening of the relaxation times below the capability limits of the NMR instrument. We proposed [3] "heating up" the molecular motion of the HMWC fragments by irradiation at their absorption wavelength, thereby increasing the frequency and amplitude of molecular motion and achieving a selective increase of the relaxation times and their observation.Our goal was to study structural and dynamic changes of molecular motion NMR parameters as a function of temperature and irradiation time in the visible and near-IR (NIR) regions and to increase the selectivity and sensitivity of the analysis of oil components.Experimental. We studied oil samples from the Romashkin deposit with densities ρ = 867-938 kg/m 3 and asphaltene concentrations 3.30-6.70 mass %. In particular, oil of density ρ = 867.5 kg/m 3 had kinematic viscosity ν 20 = 42.9 cSt and concentrations of oil 51.2%; benzene resins, 17.4; alcohol-benzene resins, 7.1; asphaltenes, 3.3; sulfur, 1.6; and paraffins, 3.1. We also studied samples of this oil to which various amounts of the paraffin docosane (C 22 H 46 ) of density ρ = 778 kg/m ...

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“…We previously demonstrated the possibilities of the nuclear magnetic resonance (NMR) method in analysis of different physicochemical and technological characteristics using different examples in [9][10][11][12][13][14][15][16][17][18][19][20]. Development of the NMRR method is needed for monitoring the droplet size distribution in emulsions of high-viscosity crude oils (bitumens) and the water concentration during formation and breakdown of the emulsions, and also to establish correlations between the NMRR parameters and the droplet size distribution in as broad a hydrocarbon density range as possible.…”

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Determination of dispersity of aqueous emulsions of hydrocarbons by nuclear magnetic resonance relaxometry

Kashaev

Faskhiev

2011

Chem Technol Fuels Oils

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We have used nuclear magnetic resonance relaxometry to study emulsions of viscous crude oils for water concentrations in the range 4.9-50.1 wt.%. We obtained the dependences of the proton relaxation parameters for the components of the emulsions (water in droplets, hydrocarbon medium, and boundary phase) on their treatment parameters and the water concentration. The experimental results are interpreted within a proposed model for the proton dynamics. We establish experimental relations between the NMR relaxation parameters and the integral diameters of the water droplets, characterizing their size distribution, for emulsions of crude oils, residual oils, and bitumens.In recent years, the volume of production has increased for high water-cut viscous sulfur crude oils and bitumens in the form of emulsions, the stability of which is determined by high content of asphaltenes, tars, sulfur, turbulent hydrodynamic conditions for movement of the borehole fluid, dispersal of the crude oil by the pumps, and use of reagents for improving oil recovery. For timely prevention of asphalt/tar/paraffin precipitation and selection of conditions for pumping and treatment of such crude oil systems, we need on-the-fly (on-line) monitoring of the concentration of asphaltenes and tars.On the other hand, fuel emulsions have become increasingly important for world energy production as an alternative to black oil for use as a fuel for thermal power plants. Thus for example, water/residual oil and water/ bitumen emulsions are less viscous, their use ensures more complete burning of carbon for low oxygen concentrations, reduction in nitrogen oxide emissions by 65%-80% and reduction of polycyclic aromatic hydrocarbon emissions. Their ash contains up to 260 mg/kg vanadium and 55 mg/kg nickel, and is used as an ore. Use of fuel emulsions makes it possible to save heavy oil fuel and requires minimal burner retrofitting. It seems that water-cut residual oils, industrial organic effluents, and "cleanup" waste from washing barges, tanks, and oil tankers might be used as fuel emulsions. The conditions for stable operation of burners based on fuel emulsions

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The influence of sulfur on the structural-dynamic parameters of petroleum systems studied by the NMR technique

Cited by 3 publications

References 2 publications

Study of Vacuum Residues and Their Transformation to Asphalts for the Pavement Industry by Nuclear Magnetic Resonance and Chemometric Methods

Study of Vacuum Residues and Their Transformation to Asphalts for the Pavement Industry by Nuclear Magnetic Resonance and Chemometric Methods

Effect of irradiation in the visual and infrared spectral regions on nuclear magnetic relaxation parameters of protons in oil products

Determination of dispersity of aqueous emulsions of hydrocarbons by nuclear magnetic resonance relaxometry

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