RESUMO
Crude oil distillates are a highly useful industrial product, mainly for energy generation. Unfortunately, they are rarely studied, mainly due to the low accessibility to products directly obtained from the distillation process, which is a laborious, expensive, and time-consuming operation. This work presents and discusses the use of time-domain nuclear magnetic resonance (TD-NMR) as a simple, affordable, and straightforward tool for the development of correlations supported on the transverse relaxation time (T2 ) and boiling temperature. The results point out a high convergence between TD-NMR experimental data and the ASTM D2892 method for distillates from light, medium, and heavy oils, with up to 52.20% of accumulated mass and boiling point temperature (Tb ) up to 400°C. Furthermore, an unprecedented relationship between T2 values and the accumulated mass of the distillates is first demonstrated. This new insight opens new perspectives for future prediction of accumulated mass for unknown crude oils, placing the TD-NMR relaxometry as an appeal spectroscopy approach with a potential to meaningfully contribute to the daily refining petrochemical industry field operations.
Assuntos
Petróleo , Petróleo/análise , Destilação , Espectroscopia de Ressonância Magnética/métodos , Imageamento por Ressonância Magnética , TemperaturaRESUMO
During the oil production and processing stages, the asphaltene precipitation is one of the great operation problems of oil industry. It can precipitate in the formation, tubing, or surface, causing operating problems, such as reduction in oil recovery by changing the reservoir permeability and wettability, clogging of the pipelines, and difficulty in separations process. The quantification of asphaltenes in petroleum by ASTM D6560 standard method is very laborious and use of a larger solvent volume than necessary. The present work proposes the use of time domain nuclear magnetic resonance (TD-NMR) as new methodology to quantify the asphaltene precipitated in crude oil. Three (light, medium, and heavy) crude oils with asphaltenes content of 0.97, 1.88, and 7.00 wt% were mixed with n-heptane in different R (ml of solvent/g of oil) values and analyzed by means of transverse relaxation time (T2 ). According NMR results, the R values enough for complete asphaltene precipitation for the oils A, B, and C were, respectively, equal to 16.50, 23.00, and 39.50 ml g-1 . These outcomes represent a reduction of 58.75%, 42.50%, and 1.25% in the solvent volume per mass of oil for the oil A, B, and C, respectively, compared to the ASTM D6560 method, which imposes 40 ml g-1 . Therefore, it has been shown that TD-NMR can be applied to estimate the amount of asphaltene precipitated in petroleum and have potential to be applied in routine analysis with advantages of saving time and costs.
RESUMO
The use of a low-cost benchtop time-domain NMR (TD-NMR) spectrometer to monitor copper electrodeposition in situ is presented. The measurements are based on the strong linear correlation between the concentration of paramagnetic ions and the transverse relaxation rates (R(2)) of the solvent protons. Two electrochemical NMR (EC-NMR) cells were constructed and applied to monitor the Cu(2+) concentration during the electrodeposition reaction. The results show that TD-NMR relaxometry using the Carr-Purcell-Meiboom-Gill pulse sequence can be a very fast, simple, and efficient technique to monitor, in real time, the variation in the Cu(2+) concentration during an electrodeposition reaction. This methodology can also be applied to monitor the electrodeposition of other paramagnetic ions, such as Ni(2+) and Cr(3+), which are commonly used in electroplating.
RESUMO
Low-field (1) H NMR was used in this work for the analysis of mixtures involving crude oils and water. CPMG experiments were performed to determine the transverse relaxation time (T2 ) distribution curves, which were computed by the inverse Laplace transform of the echo decay data. The instrument's ability of quantifying water and petroleum in biphasic mixtures following different methodologies was tested. For mixtures between deionized water and petroleum, one achieved excellent results, with root mean squared error of cross-validation (RMSECV) of 0.8% for a regression between the water content (wt %) and the relative area of the water peak in the T2 distribution curve, or a standard deviation of 0.9% for the relationship between the water content and the relative water peak area, corrected by the relative hydrogen index of the crude. In the case of biphasic mixtures of Mn(2+) -doped water and crude oils, the best result of RMSECV = 1.6% was achieved by using the raw magnetization decay data for a partial least squares regression.
RESUMO
All attempts to use in situ(13)C NMR in spectroelectrochemical studies, using static cells and unlabeled substrates, have failed due to the very long average time (several hours). In this paper, we demonstrated that steady-state free precession (SSFP) pulse sequence can enhance signal to noise ratio and reduces the average time of (13)C NMR signals by more than one order of magnitude. The results showed that each (13)C NMR spectrum during the electrochemical reduction of 9-chloroanthracene, in a static cell, can be acquired in eleven minutes. This short averaging time allowed the analysis of the reaction every 30min during 3h. The phase and truncation anomalies present in SSFP spectra were minimized using Traff apodization function and Krylov basis diagonalization method (KBDM).