Multi-dimensional Nuclear Magnetic Resonance Characterizations of Dynamics and Saturations of Brine/Crude Oil/Mud Filtrate Mixtures Confined in Rocks: The Role of Asphaltene

Benamsili, Lyès; Korb, Jean-Pierre; Hamon, Gérald; Louis‐Joseph, Alain; Bouyssière, Brice; Zhou, Honggang; Bryant, Robert G.

doi:10.1021/ef401871h

Cited by 39 publications

(92 citation statements)

References 27 publications

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“…We used the Topspin software of Bruker for data processing. The T 2 distributions show a bimodal distribution as consistent with our previous results from gas chromatography GC and gel permeation chromatography GPC 20 . In native crude oil with 9 % wt asphaltene, we noticed a similar distribution shape between T 2 and GC and GPC.…”

Section: High Field 2d Nmr Dosysupporting

confidence: 91%

“…These two equations have been correlated by varying the viscosity in the range {1-40 cp} for different representative gyration radii R agg of asphaltene macroaggregates 1.0, 1.5, 2.0 and 2.6 nm. The colored continuous lines in Figure 7 represent the theoretical fits obtained for various representative radii of the asphaltene macroaggregates with application of the model of quasi 1D diffusional dynamics of long hydrocarbons in between the slowly rotating asphaltene macroaggregates 20 . One sees that these fits reproduce quite well the essential features of the experimental data of Figure 6a as well as the Figure 6 of ref.…”

Section: Longitudinal-transverse Relaxation (T 1 -T 2 ) Maps 2d T 1 mentioning

confidence: 99%

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Probing Dynamics and Interaction of Maltenes with Asphaltene Aggregates in Crude Oils by Multiscale NMR

et al. 2015

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Asphaltenes cause many problems in crude oil transportation, refinery and production. A clear understanding of asphaltene behavior in crude oils is thus crucial for improving crude oil production. Here, we used noninvasive multiscale NMR techniques such as low field NMR 2D D-T 2 , T 1 -T 2 , nuclear magnetic relaxation dispersion (NMRD) techniques as well as high field 2D NMR DOSY for probing the dynamics and interaction of maltenes with asphaltene aggregates in crude oil. We prepared different asphaltene concentrations ranging between 0% wt (pure maltenes) and 9% wt (native crude oil) by using a dilution procedure that maintains the asphaltene aggregates structure initially present in native crude oil. We showed by multiscale NMR techniques that changing asphaltene concentration induces a drastic modification of hydrocarbon dynamics. In native crude oil, we observe anomalous relation between the diffusion coefficient (D) and the transverse relaxation time (T 2 ) that we can reproduce theoretically by a quasi 1D diffusion of hydrocarbons in between slowly rotating asphaltene macroaggregates. The relation D α T 2 usually observed in crude oils without asphaltenes was progressively appearing when asphaltene concentration decreased. Our 2D D-T 2 results at 2.5 and 23 MHz show that the diffusion coefficient varies by a factor 4 while the T 2 changes by more than an order of magnitude when the asphaltene concentrations vary. These observations prove that the hydrocarbon dynamics changes drastically at nanoscale and vary much less at large length scales (µm). Moreover, the 2D D-T 2 also shows two different dynamics for short and long chain hydrocarbons in crude oil. This is confirmed by high field 2D NMR DOSY. We found also that the ratio T 1 /T 2 in 2D T 1 -T 2 distribution was progressively reduced when asphaltene concentration decrease with an upward bent away in native crude oil at short T 2 that we succeeded to interpret with the quasi 1D hydrocarbon dynamics. We observed that the NMRD profiles are completely different for crude oil with and without asphaltenes. In native crude oil, NMRD techniques clearly evidence a 2D translational diffusion of short hydrocarbon chains at proximity of the asphaltene nanoaggregates. In crude oil without asphaltene, the NMRD profile is explained in term of a rotational reorientation of hydrocarbon chains. Most of our proposed multiscale NMR techniques could be made down-hole and then can give an invaluable tool for a clear understanding of asphaltene behavior in crude oil.

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Section: High Field 2d Nmr Dosysupporting

confidence: 91%

Section: Longitudinal-transverse Relaxation (T 1 -T 2 ) Maps 2d T 1 mentioning

confidence: 99%

Probing Dynamics and Interaction of Maltenes with Asphaltene Aggregates in Crude Oils by Multiscale NMR

et al. 2015

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“…The other components in crude oils such as ''saturated", ''aromatic" and ''resin" components of the SARA analysis [107] are soluble in nalkane solvents and defined as maltenes. There are also different paramagnetic species in crude oils that have a great importance in the NMR measurements such as vanadyl ions VO 2+ and organic carbon radicals that can be clearly identified by ESR spectra [111,112]. Our main objective here is to review how NMRD and 2D T 1 -T 2 or D-T 2 techniques can be useful for characterizing, on different length-and time-scales, the dynamical properties of hydrocarbons in presence or absence of asphaltenes.…”

Section: Applications To Petroleum Fluidsmentioning

confidence: 99%

Multiscale nuclear magnetic relaxation dispersion of complex liquids in bulk and confinement

Korb

2018

Progress in Nuclear Magnetic Resonance Spectroscopy

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The nuclear magnetic relaxation dispersion (NMRD) technique consists of measurement of the magnetic-field dependence of the longitudinal nuclear-spin-lattice relaxation rate 1/T. Usually, the acquisition of the NMRD profiles is made using a fast field cycling (FFC) NMR technique that varies the magnetic field and explores a very large range of Larmor frequencies (10 kHz < ω/(2π) <40 MHz). This allows extensive explorations of the fluctuations to which nuclear spin relaxation is sensitive. The FFC technique thus offers opportunities on multiple scales of both time and distance for characterizing the molecular dynamics and transport properties of complex liquids in bulk or embedded in confined environments. This review presents the principles, theories and applications of NMRD for characterizing fundamental properties such as surface correlation times, diffusion coefficients and dynamical surface affinity (NMR wettability) for various confined liquids. The basic longitudinal and transverse relaxation equations are outlined for bulk liquids. The nuclear relaxation of a liquid confined in pores is considered in detail in order to find the biphasic fast exchange relations for a liquid at proximity of a solid surface. The physical-chemistry of liquids at solid surfaces induces striking differences between NMRD profiles of aprotic and protic (water) liquids embedded in calibrated porous disordered materials. A particular emphasis of this review concerns the extension of FFC NMR relaxation to industrial applications. For instance, it is shown that the FFC technique is sufficiently rapid for following the progressive setting of cement-based materials (plasters, cement pastes, concretes). The technique also allows studies of the dynamics of hydrocarbons in proximity of asphaltene nano-aggregates and macro-aggregates in heavy crude oils as a function of the concentration of asphaltenes. It also gives new information on the wettability of petroleum fluids (brine and oil) embedded in shale oil rocks. It is useful for understanding the relations and correlations between NMR relaxation times T and T, diffusion coefficients D, and viscosity η of heavy crude oils. This is of particular importance for interpreting T, T, 2D T-T and D-T correlation spectra that could be obtained down-hole, thus giving a valuable tool for investigating in situ the molecular dynamics of petroleum fluids. Another domain of interest concerns biological applications. This is of particular importance for studying the complex dynamical spectrum of a folded polymeric structure that may span many decades in frequency or time. A direct NMRD characterization of water diffusional dynamics is presented at the protein interface. NMR experiments using a shuttle technique give results well above the frequency range accessible via the FFC technique; examples of this show protein dynamics over a range from fast and localized motions to slow and delocalized collective motions involving the whole protein. This review ends by an interpretation of the origin of the proto...

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“…and even, in the worst cases, stop the fluid production (plugging pores in the reservoir, well-bore tubing or flow-lines/pipelines, accumulating in separators, etc.). 3 Asphaltenes consist of a complex mixture of polycyclic aromatic hydrocarbons substituted with alkyl side chains and the presence of heteroatoms, like nitrogen, sulfur and oxygen is common on the conjugated core. 4 Moreover, porphyrines are also found in this petroleum phase, including the ones having nickel, vanadium and chromium as metallic centers.…”

Section: Introductionmentioning

confidence: 99%

Molecular Dynamics Study of Nanoaggregation in Asphaltene Mixtures: Effects of the N, O, and S Heteroatoms

et al. 2016

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In this paper the aggregation of asphaltenes is studied for two asphaltene molecule families, namely PA3 and CA22 analogues, based on the work of Schuler et al. (JACS, 2015, 137, 31, 9870). The chemical characteristics of these molecules were screened by changing the heteroatoms on the backbone and the lateral chain-ends. These molecules were mixed together with different relative concentrations and for the first time the aggregation of different asphaltenes was determined using molecular dynamics simulations (MDS). The results show that the interaction energies vary for different heteroatom arrangement within a given structure and depend on the type of asphaltene. Moreover, we showed that the chain-ends have a crucial role on this phenomenon.

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Multi-dimensional Nuclear Magnetic Resonance Characterizations of Dynamics and Saturations of Brine/Crude Oil/Mud Filtrate Mixtures Confined in Rocks: The Role of Asphaltene

Abstract: International audienceno abstrac

Cited by 39 publications

References 27 publications

Probing Dynamics and Interaction of Maltenes with Asphaltene Aggregates in Crude Oils by Multiscale NMR

Probing Dynamics and Interaction of Maltenes with Asphaltene Aggregates in Crude Oils by Multiscale NMR

Multiscale nuclear magnetic relaxation dispersion of complex liquids in bulk and confinement

Molecular Dynamics Study of Nanoaggregation in Asphaltene Mixtures: Effects of the N, O, and S Heteroatoms

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